EP0450437B1 - Copolymers based on C1-C8-alkyl-acrylates and/or methacrylates, process for their preparation and their use - Google Patents
Copolymers based on C1-C8-alkyl-acrylates and/or methacrylates, process for their preparation and their use Download PDFInfo
- Publication number
- EP0450437B1 EP0450437B1 EP91104620A EP91104620A EP0450437B1 EP 0450437 B1 EP0450437 B1 EP 0450437B1 EP 91104620 A EP91104620 A EP 91104620A EP 91104620 A EP91104620 A EP 91104620A EP 0450437 B1 EP0450437 B1 EP 0450437B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- weight
- polyvinyl alcohol
- water
- copolymers
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 229920001577 copolymer Polymers 0.000 title claims description 60
- 238000000034 method Methods 0.000 title description 7
- 150000002734 metacrylic acid derivatives Chemical class 0.000 title description 6
- 238000002360 preparation method Methods 0.000 title description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 55
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 47
- 229920000728 polyester Polymers 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 21
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 12
- 125000003118 aryl group Chemical group 0.000 claims description 10
- 239000000178 monomer Substances 0.000 claims description 10
- 238000007720 emulsion polymerization reaction Methods 0.000 claims description 9
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 7
- 239000000654 additive Substances 0.000 claims description 7
- 239000000835 fiber Substances 0.000 claims description 7
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 6
- 239000000839 emulsion Substances 0.000 claims description 6
- 150000001735 carboxylic acids Chemical class 0.000 claims description 5
- 238000010528 free radical solution polymerization reaction Methods 0.000 claims description 5
- 229910052783 alkali metal Inorganic materials 0.000 claims description 4
- 150000003863 ammonium salts Chemical class 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- 150000001340 alkali metals Chemical class 0.000 claims description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 3
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 3
- 150000008064 anhydrides Chemical class 0.000 claims description 3
- 150000003839 salts Chemical group 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- 229920001410 Microfiber Polymers 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- 239000003658 microfiber Substances 0.000 claims description 2
- 150000003254 radicals Chemical class 0.000 claims 2
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 41
- 238000004513 sizing Methods 0.000 description 33
- 239000000243 solution Substances 0.000 description 30
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 27
- 239000012188 paraffin wax Substances 0.000 description 25
- 239000003795 chemical substances by application Substances 0.000 description 24
- BWYYYTVSBPRQCN-UHFFFAOYSA-M sodium;ethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=C BWYYYTVSBPRQCN-UHFFFAOYSA-M 0.000 description 24
- 229920000642 polymer Polymers 0.000 description 18
- 229920002959 polymer blend Polymers 0.000 description 18
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 14
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 14
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 14
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 12
- -1 aromatic dicarboxylic acids Chemical class 0.000 description 12
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 12
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 12
- 230000000694 effects Effects 0.000 description 11
- YAJYJWXEWKRTPO-UHFFFAOYSA-N 2,3,3,4,4,5-hexamethylhexane-2-thiol Chemical compound CC(C)C(C)(C)C(C)(C)C(C)(C)S YAJYJWXEWKRTPO-UHFFFAOYSA-N 0.000 description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 10
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 9
- 238000006116 polymerization reaction Methods 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 7
- 239000000853 adhesive Substances 0.000 description 7
- 230000001070 adhesive effect Effects 0.000 description 7
- 239000003995 emulsifying agent Substances 0.000 description 7
- 239000003999 initiator Substances 0.000 description 7
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 6
- 230000007062 hydrolysis Effects 0.000 description 6
- 238000006460 hydrolysis reaction Methods 0.000 description 6
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 6
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 5
- 230000000903 blocking effect Effects 0.000 description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 5
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 150000002009 diols Chemical class 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 238000006386 neutralization reaction Methods 0.000 description 4
- 229920002689 polyvinyl acetate Polymers 0.000 description 4
- 239000011118 polyvinyl acetate Substances 0.000 description 4
- 229920000742 Cotton Polymers 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- 238000009941 weaving Methods 0.000 description 3
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 2
- YZTJKOLMWJNVFH-UHFFFAOYSA-N 2-sulfobenzene-1,3-dicarboxylic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1S(O)(=O)=O YZTJKOLMWJNVFH-UHFFFAOYSA-N 0.000 description 2
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 2
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- 239000005642 Oleic acid Substances 0.000 description 2
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 2
- 229920000297 Rayon Polymers 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCCCC1 ORLQHILJRHBSAY-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- WQAQPCDUOCURKW-UHFFFAOYSA-N butanethiol Chemical compound CCCCS WQAQPCDUOCURKW-UHFFFAOYSA-N 0.000 description 2
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 2
- 239000004816 latex Substances 0.000 description 2
- 229920000126 latex Polymers 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 2
- HJUGFYREWKUQJT-UHFFFAOYSA-N tetrabromomethane Chemical compound BrC(Br)(Br)Br HJUGFYREWKUQJT-UHFFFAOYSA-N 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 239000002562 thickening agent Substances 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- ALSTYHKOOCGGFT-KTKRTIGZSA-N (9Z)-octadecen-1-ol Chemical compound CCCCCCCC\C=C/CCCCCCCCO ALSTYHKOOCGGFT-KTKRTIGZSA-N 0.000 description 1
- DMWVYCCGCQPJEA-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane Chemical compound CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C DMWVYCCGCQPJEA-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- FLZDRQXGVYVYSL-UHFFFAOYSA-N 3-(2-cyanopropyldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)CN=NCC(C)C#N FLZDRQXGVYVYSL-UHFFFAOYSA-N 0.000 description 1
- CGTLMVREWQIWEC-UHFFFAOYSA-N 4-decylphenol Chemical compound CCCCCCCCCCC1=CC=C(O)C=C1 CGTLMVREWQIWEC-UHFFFAOYSA-N 0.000 description 1
- IGFHQQFPSIBGKE-UHFFFAOYSA-N 4-nonylphenol Chemical compound CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- PQUCIEFHOVEZAU-UHFFFAOYSA-N Diammonium sulfite Chemical compound [NH4+].[NH4+].[O-]S([O-])=O PQUCIEFHOVEZAU-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-N Propionic acid Chemical group CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 1
- 229910006069 SO3H Inorganic materials 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical group 0.000 description 1
- 125000005250 alkyl acrylate group Chemical group 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- ZETCGWYACBNPIH-UHFFFAOYSA-N azane;sulfurous acid Chemical compound N.OS(O)=O ZETCGWYACBNPIH-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- AGEZXYOZHKGVCM-UHFFFAOYSA-N benzyl bromide Chemical compound BrCC1=CC=CC=C1 AGEZXYOZHKGVCM-UHFFFAOYSA-N 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- XNNQFQFUQLJSQT-UHFFFAOYSA-N bromo(trichloro)methane Chemical compound ClC(Cl)(Cl)Br XNNQFQFUQLJSQT-UHFFFAOYSA-N 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 1
- MOTZDAYCYVMXPC-UHFFFAOYSA-N dodecyl hydrogen sulfate Chemical compound CCCCCCCCCCCCOS(O)(=O)=O MOTZDAYCYVMXPC-UHFFFAOYSA-N 0.000 description 1
- 229940043264 dodecyl sulfate Drugs 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 230000009969 flowable effect Effects 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- 238000010327 methods by industry Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 1
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical compound CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 0.000 description 1
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 229940055577 oleyl alcohol Drugs 0.000 description 1
- XMLQWXUVTXCDDL-UHFFFAOYSA-N oleyl alcohol Natural products CCCCCCC=CCCCCCCCCCCO XMLQWXUVTXCDDL-UHFFFAOYSA-N 0.000 description 1
- 229940113162 oleylamide Drugs 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- DJEHXEMURTVAOE-UHFFFAOYSA-M potassium bisulfite Chemical compound [K+].OS([O-])=O DJEHXEMURTVAOE-UHFFFAOYSA-M 0.000 description 1
- 235000010259 potassium hydrogen sulphite Nutrition 0.000 description 1
- 229940096992 potassium oleate Drugs 0.000 description 1
- BHZRJJOHZFYXTO-UHFFFAOYSA-L potassium sulfite Chemical compound [K+].[K+].[O-]S([O-])=O BHZRJJOHZFYXTO-UHFFFAOYSA-L 0.000 description 1
- 235000019252 potassium sulphite Nutrition 0.000 description 1
- MLICVSDCCDDWMD-KVVVOXFISA-M potassium;(z)-octadec-9-enoate Chemical compound [K+].CCCCCCCC\C=C/CCCCCCCC([O-])=O MLICVSDCCDDWMD-KVVVOXFISA-M 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229940079827 sodium hydrogen sulfite Drugs 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- OPQYOFWUFGEMRZ-UHFFFAOYSA-N tert-butyl 2,2-dimethylpropaneperoxoate Chemical compound CC(C)(C)OOC(=O)C(C)(C)C OPQYOFWUFGEMRZ-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000009988 textile finishing Methods 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 150000003628 tricarboxylic acids Chemical class 0.000 description 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/327—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated alcohols or esters thereof
- D06M15/333—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated alcohols or esters thereof of vinyl acetate; Polyvinylalcohol
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F261/00—Macromolecular compounds obtained by polymerising monomers on to polymers of oxygen-containing monomers as defined in group C08F16/00
- C08F261/02—Macromolecular compounds obtained by polymerising monomers on to polymers of oxygen-containing monomers as defined in group C08F16/00 on to polymers of unsaturated alcohols
- C08F261/04—Macromolecular compounds obtained by polymerising monomers on to polymers of oxygen-containing monomers as defined in group C08F16/00 on to polymers of unsaturated alcohols on to polymers of vinyl alcohol
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
Definitions
- the invention relates to the copolymers completely or partially neutralized with alkali metal, alkaline earth metal and ammonium salts, a process for the preparation of the copolymers, their use as a means for the temporary surface protection of shaped bodies and flat structures and as a sizing agent for the processing of staple fiber and filament yarns as well as these sizing agents.
- the invention relates to sizing agents from the described acrylate and / or methacrylate copolymers, polyvinyl alcohol, customary additives and completely or partially neutralized, sulfo and / or carboxyl group-containing, salt-form water-soluble polyesters of non-aromatic C2-C6 diols and mixtures of aromatic dicarboxylic acids and aromatic Tricarboxylic acids and / or sulfodicarboxylic acids and the use of these sizing agents for the processing of filament yarns.
- Copolymers prepared by emulsion polymerization in the presence of protective colloids such as polyvinyl alcohol and based on alkyl acrylates and / or methacrylates with minor amounts of other comonomers such as unsaturated carboxylic acids, e.g. Acrylic acid, are known from various publications.
- the copolymers in the other hand contain a maximum of 7% (US Pat. No. 3,876,596), a maximum of 5% (US Pat. No. 4,670,505) or a maximum of 2% (US Pat. No. 4,265,796) ) very little polyvinyl alcohol as a protective colloid.
- copolymers described have an undesired sticking of the sized filament threads and experience a large increase in viscosity during neutralization.
- the recording materials are produced, for example, by coating plastic films with an aqueous coating composition which contains a pigment and a binder as essential constituents.
- the binder consists of a polymer that is produced by reacting polyvinyl alcohol with methyl methacrylate and acrylic acid.
- the polymer contains 3 to 20 wt .-% acrylic acid and the ratio of polyvinyl alcohol to methyl methacrylate is 95: 5 to 10: 90.
- GB-A-1 438 449 discloses the emulsion polymerization of acrylates, methacrylates and butadiene in the presence of hydrolyzed vinyl acetate / alkali metal olefin sulfonate copolymers.
- the acrylates and methacrylates can also be copolymerized in a mixture with acrylic acid or methacrylic acid.
- the aqueous polymer dispersions obtainable in this way can be used, for example, as an adhesive, coating agent, extraordinarilyl or paper auxiliary.
- the object of the present invention is to provide new sizing agents.
- Sizing agents from the described acrylate and / or methacrylate copolymers, polyvinyl alcohol, customary additives and completely or partially neutralized sulfo and / or carboxyl groups containing salt-water-soluble polyesters from non-aromatic C2-C6 diols and mixtures of aromatic dicarboxylic acids and Wegn tricarboxylic acids and / or -sulfodicarboxylic acids found.
- the copolymers to be used according to the invention are from 50 to 95 wt .-%, preferably 70 to 80 wt .-% of a C1-C8 alkyl acrylate and / or methacrylate as component A and 5 to 20 wt .-% of an unsaturated carboxylic acid as a component B in the presence of 2 to 60 parts by weight, preferably 10 to 40 parts by weight of polyvinyl alcohol, based on 100 parts by weight of A and B.
- copolymers to be used according to the invention can also be built up from up to 20% by weight of further water-soluble comonomers as component C and from up to 10% by weight of other comonomers as component D.
- component A are C1-C8 alkyl acrylates and / or methacrylates.
- Particularly preferred components A are methyl and n-butyl acylate and / or methacrylate.
- Ethyl, n-propyl, iso-propyl, iso-butyl, sec-butyl, tert-butyl acrylate or methacrylate are preferred.
- n-pentyl, n-hexyl, 2-ethylhexyl, n-heptyl and n-octyl acrylate or methacrylate are mentioned.
- unsaturated carboxylic acids come into consideration primarily acrylic acid and methacrylic acid.
- Crotonic acid, maleic acid, fumaric acid, itaconic acid and the anhydrides of unsaturated carboxylic acids are also suitable.
- Additional water-soluble comonomers as component C are, above all, acrylamide, methacrylamide, allyl alcohol and very particularly acrylonitrile and sodium vinyl sulfonate.
- component D preferably vinyl aromatics such as styrene, vinyl acetate, vinyl propionate, N-vinylpyrrolidone and the esters of unsaturated dicarboxylic acids such as the di-n-butyl ester of maleic acid.
- vinyl aromatics such as styrene, vinyl acetate, vinyl propionate, N-vinylpyrrolidone and the esters of unsaturated dicarboxylic acids such as the di-n-butyl ester of maleic acid.
- the polyvinyl alcohols used as component E preferably have a degree of polymerization of 200 to 2000 and a degree of hydrolysis of 75 to 99 mol%. The remaining 1 to 25 mol% are accounted for by acetate or propionate groups of the polyvinyl acetate or propionate preferably used for the production of the polyvinyl alcohol.
- polyvinyl alcohols with a degree of polymerization of 300 to 2000 (corresponding to a standard viscosity of 3 to 25 mPa ⁇ s) and a degree of saponification of 86 to 90 mol% are preferred.
- copolymers to be used according to the invention are prepared by free-radical solution polymerization, preferably by free-radical emulsion polymerization in aqueous solution.
- the usual peroxo or azo compounds can be used as initiators for the radical polymerization reaction Reducing agents, advantageously in amounts of 0.5 to 2.0 wt .-%, based on the weight of the monomers.
- Preferred initiators are dibenzoyl peroxide, tert-butyl perpivalate, tert-butyl per-2-ethylhexanoate, di-tert-butyl peroxide, tert-butyl hydroperoxide, 2,5-dimethyl-2,5-di (tert-butyl peroxy) hexane To name cumene hydroperoxide and 4,4'-azobisisobutyronitrile.
- Preferred reducing agents are hydrazine, sodium sulfite, sodium hydrogen sulfite, potassium sulfite, potassium hydrogen sulfite, ammonium sulfite and ammonium hydrogen sulfite, which are used in amounts of 0.005 to 2.0% by weight.
- Preferred emulsifiers are anionic emulsifiers such as lauryl sulfate, p-n-nonylphenol, p-n-decylphenol, sodium stearate, potassium oleate and especially C15 paraffin sulfonate.
- Suitable nonionic emulsifiers are preferably the oxyethylation products of lauryl alcohol, oleyl alcohol, stearyl alcohol, oleic acid and stearic amide, oleyl amide and stearic and oleic acid with a degree of oxyethylation of 3 to 20.
- cationic emulsifiers such as ammonium, phosphonium and sulfonium compounds are also suitable a long aliphatic hydrocarbon chain as a hydrophobic part of the molecule.
- the emulsifiers important for emulsion polymerization are used in amounts of 0.1 to 2.0% by weight.
- Regulators can be added to control the molecular mass. It is particularly important to use a regulator with larger quantities of polyvinyl alcohol, since without a regulator it is possible to form highly viscous, non-flowable solutions that are less suitable as sizing agents.
- Preferred regulators are carbon tetrachloride, carbon tetrabromide, benzyl bromide, trichlorobromomethane and butyl mercaptan, which are generally used in amounts of 0.1 to 5% by weight.
- tert. -Dodecyl mercaptan as a regulator in amounts of 0.2 to 1.0% by weight in combination with 1.0 to 1.5% by weight of a peroxo compound as an initiator.
- the polymerization is carried out at 20 to 95 ° C., preferably at 65 to 90 ° C.
- reaction is expediently carried out at normal pressure, but it is also possible to work under reduced or slightly increased pressure, that is to say in the range from 0.5 to 5 bar.
- the reaction times are usually 1 to 5, usually 2 to 3 hours.
- the emulsion feed process is generally carried out in such a way that an aqueous solution of some of the initiators, emulsifiers and regulators is heated to the reaction temperature and the monomers are fed in the same or changing proportions, preferably continuously. It is also possible to add a portion of the monomers, preferably 4 to 20% by weight, to start the polymerization and to start adding the majority of the monomer mixture after about 10 to 30 minutes.
- the polyvinyl alcohol can be added at the same time or with a time lag with the monomers; amounts of up to 10% by weight are preferably introduced in the aqueous solution.
- the remaining portions of the initiators, emulsifiers and regulators are added continuously or intermittently.
- the polymerization is expediently continued, with the addition of further amounts of initiator, for a period of about 1 hour in order to lower residual monomer contents.
- the copolymers are preferably converted into their sodium, calcium, magnesium, ammonium or C1-C4-alkylammonium salts at temperatures between 50 and 85 ° C.
- the proportion of the salts is at least 50%.
- the aqueous latex is preferably treated with aqueous ammonia.
- Staple fiber sizing is preferably obtained by adding sodium hydroxide solution, sodium carbonate or sodium hydrogen carbonate to the aqueous latex.
- solutions thus obtainable can be used directly or together with other components as sizing agents for polyester, cellulose acetate, polyamide, viscose, cotton, cotton / polyester, viscose / polyester and for polyester / wool fibers.
- polyesters defined as component c) are known or can be obtained by known methods (Ullmann, Vol. 23, p. 17 (1983).
- non-aromatic C2-C6 diols such as diethylene glycol or 1,4-hydroxymethylcyclohexane and a mixture of an aromatic dicarboxylic acid such as isophthalic acid or terephthalic acid and an aromatic tricarboxylic acid and / or sulfodicarboxylic acid such as trimellitic acid and / or sulfoisophthalic acid.
- Polyesters with molecular weights of 150,000 to 250,000 and an acid number of 40 to 60 mg of potassium hydroxide per free polymer are preferably used.
- Thickeners, pigments, crosslinking agents, fillers, reinforcing agents, filming aids and antioxidants are also suitable.
- the polymer mixtures according to the invention are preferably produced by combining acrylate and / or methacrylate copolymers, polyvinyl alcohol, polyester and optionally conventional additives as a 15 to 25% by weight solution.
- the copolymers and polymer mixtures according to the invention preferably have K values of 25 to 120, particularly 30 to 50.
- the desired K value in each case can be set in a manner known per se by choosing the polymerization conditions, primarily the duration of the polymerization and the initiator concentration.
- the K values are measured according to Fikentscher, Cellulose-Chemie, Vol. 13, pp. 58 to 64 (1932) at 25 ° C in 0.5% by weight tetrahydrofuran solution and represent a measure of the molecular weight.
- the dispersions or solutions of the copolymers and polymer mixtures according to the invention have solids contents of preferably 20 to 50% by weight, the partially neutralized or neutralized dispersions or solutions preferably have solids contents of 18 to 25% by weight.
- copolymers according to the invention are mainly used as sizing agents for processing staple fiber and filament yarns
- the polymer mixtures according to the invention are preferably used as sizing agents for processing microfiber yarns, multifilament yarns and textured or smooth filament yarns.
- They can also be used to temporarily protect the surface of flat or spatial structures, such as drawings, maps, prints, photos or images.
- copolymers according to the invention are notable for their good sizing effect, while at the same time having a high film hardness and hence a low tendency to stick together the sized filament threads. Furthermore they show high adhesive strength values as well as mixture stability and low viscosity. A particular advantage of these copolymers is that they can be easily washed out before further processing of the yarns.
- the viscosities of the copolymers given in the examples were measured in a Brookfield viscometer at 100 rpm and a temperature of 20 ° C. in aqueous solution at the concentrations given in each case.
- copolymers prepared according to methods a) and b) were obtained in the form of aqueous dispersions by the emulsion polymerization process. After addition of a base, the copolymer dispersed in water dissolved in each case with the formation of clear aqueous copolymer solutions.
- the mixture was then polymerized for 1 hour, cooled to 55 ° C and neutralized to pH 7.4 with 15% aqueous sodium hydroxide solution.
- the solution obtained had a polymer content of 20.6% by weight and a viscosity of 2450 mPa ⁇ s at 20 ° C.
- This copolymer was prepared analogously to Example 1 with the following template and feeds 1 and 2. 600.5 g water 0.36 g of a C-15 paraffin sulfonate 1.4 g sodium vinyl sulfonate 10 g polyvinyl alcohol 25.7 g feed 2
- the solution obtained had a polymer content of 25.1% by weight and a viscosity of 166 mPa ⁇ s at 20 ° C.
- This copolymer was prepared analogously to Example 1 with the following template and feeds 1 and 2. 842 g water 0.36 g of a C-15 paraffin sulfonate 1.4 g sodium vinyl sulfonate 20 g polyvinyl alcohol 25.5 g feed 2
- the solution obtained had a polymer content of 21.7% by weight and a viscosity of 298 mPa ⁇ s at 20 ° C.
- This copolymer was prepared analogously to Example 1 with the following template and feeds 1 and 2. 832.5 g water 0.36 g of a C-15 paraffin sulfonate 1.4 g sodium vinyl sulfonate 25.7 g feed 2
- the solution obtained had a polymer content of 20.3% by weight and a viscosity of 1660 mPa ⁇ s at 20 ° C.
- This copolymer was prepared analogously to Example 1 with the following template and feeds 1 and 2. 400.3 g of water 0.2 g of a C-15 paraffin sulfonate 0.8 g sodium vinyl sulfonate 25.4 g feed 2.
- the solution obtained had a polymer content of 20.5% by weight and a viscosity of 1640 mPa ⁇ s at 20 ° C.
- the film properties and the pilling values and the pseudo warp thread break values were determined as the application properties of the copolymers according to the invention and as a measure of the sizing effect.
- yarns of polyester / cotton in a weight ratio of 65:35 were sized at room temperature with 15% liquors of the copolymers on a laboratory sizing machine (DE-PS 2 714 897). The sized yarns were then held at 68% relative humidity and 20 ° C for 24 hours.
- Table 1 shows the results of tests A and B on the film properties and the sizing effect.
- the copolymers 1 to 5 according to the invention are completely tough, elastic and homogeneous and have high pilling and pseudo warp thread break values with regard to the sizing effect.
- This copolymer was prepared analogously to Example 1 with the following in the template and feeds 1 and 2. However, the neutralization was carried out with 25% aqueous ammonia. 873.5 g water 0.36 g of a C-15 paraffin sulfonate 1.4 g sodium vinyl sulfonate 25.7 g feed 2
- the solution obtained had a polymer content of 20.7% by weight and a viscosity of 1800 mPa ⁇ s at 20 ° C.
- This copolymer was prepared analogously to Example 6 with the following template and feeds 1 and 2. 873.5 g water 0.36 g of a C-15 paraffin sulfonate 1.4 g sodium sulfonate 25.7 g feed 2
- the solution obtained had a polymer content of 19.6% by weight and a viscosity of 152 mPa ⁇ s at 20 ° C.
- the thread closure and the tendency to blocking were determined as the application properties of the copolymers according to the invention.
- the thread closure is a measure of the quality of a size in relation to the protection and stabilization of the thread.
- the Shirley filament counter is used to determine the thread closure by cutting the filament thread before and after finishing and determining the number of free, unglued individual filaments from the pulses counted during cutting.
- the raw yarn has a manra value of 100, i.e. 100% of the individual filaments are unglued.
- the lower the manra value the more individual filaments are glued to the interface and the better the thread closure and the thread adhesion and thus the achievable weaving effect.
- test yarns made of polyester filament, smooth, dtex 50 f 18 with 6% size layer were used, which were both measured directly with the Shirley filament counter (Manra value M0 in Table 2), as well as 200 stress cycles were exposed before the measurement on the Reutlingen web tester (Manra value M200 in Table 2).
- Blocking is an undesired sticking of the cut filament threads.
- sized filament bundles with a size of 6 to 7% by weight were placed between two glass plates of 5 x 5 cm in size under pressure of an attached weight of 1 kg at 65% relative humidity and 21 ° C. for the duration of Stored for 3 days.
- Table 2 shows the results of tests A and B and the proportion of polyvinyl alcohol in the copolymers of Examples 6 and 7.
- copolymers 6 and 7 according to the invention show good thread closure without a tendency to block.
- Table 2 Application properties of the copolymers according to Examples 6 and 7 Sizing agents PVA [%] Thread closure Blocking M0 M200 according to example 6 19th 20th 29 No according to example 7 10th 15 33 No
- This copolymer was prepared analogously to Example 6 with the following template and feeds 1 and 2. 734.5 g water 0.36 g of a C-15 paraffin sulfonate 1.4 g sodium vinyl sulfonate 10.0 g polyvinyl alcohol 107.8 g feed 1
- the solution obtained had a polymer content of 24.2% by weight and a viscosity of 110 mPa ⁇ s at 20 ° C.
- This copolymer was prepared analogously to Example 6 with the following template and feeds 1 and 2. 873.5 g water 0.36 g of a C-15 paraffin sulfonate 1.4 g sodium vinyl sulfonate 20 g polyvinyl alcohol 138.1 g feed 2
- the solution obtained had a polymer content of 20.1% by weight and a viscosity of 128 mPa ⁇ s at 20 ° C.
- This copolymer was prepared analogously to Example 6 with the following template and feeds 1 and 2. 873.5 g water 0.36 g of a C-15 paraffin sulfonate 1.4 g sodium vinyl sulfonate 161.7 g feed 1
- the solution obtained had a polymer content of 19.6% by weight and a viscosity of 152 mPa ⁇ s at 20 ° C.
- This copolymer was prepared analogously to Example 6 with the following template and feeds 1 and 2. 873.5 g water 0.36 g of a C-15 paraffin sulfonate 1.4 g sodium vinyl sulfonate 174.7 g feed 1
- the solution obtained had a polymer content of 20.4% by weight and a viscosity of 1620 mPa ⁇ s at 20 ° C.
- This copolymer was prepared analogously to Example 6 with the following template and feeds 1 and 2. 873.5 g water 0.36 g of a C-15 paraffin sulfonate 1.4 g sodium vinyl sulfonate 190 g feed 1
- the solution obtained had a polymer content of 20.6% by weight and a viscosity of 1400 mPa ⁇ s at 20 ° C.
- This polyester with -COOH groups was obtained by condensation of 1 mole of diethylene glycol 0.54 mol cyclohexanedimethanol (1,4-hydroxymethylcyclohexane) 1.12 moles of isophthalic acid 0.2 mole of terephthalic acid 0.23 mole trimellitic anhydride manufactured.
- the neutralization was carried out with ammonia / triethanolamine in a ratio of 6: 4.
- This polyester with -SO3H groups was by condensation of 0.86 mole of diethylene glycol 0.2 mol cyclohexanedimethanol (1,4-hydroxymethylcyclohexane) 0.23 mole of isophthalic acid 0.70 mole of terephthalic acid 0.13 mole of sulfoisophthalic acid manufactured.
- the neutralization was carried out with sodium salt up to pH 5.6.
- the thread closure values were determined as a performance characteristic of the polymer mixtures according to the invention.
- Table 3 shows the results of this test and the chemical composition in polymer mixtures 8 to 11.
- the corresponding individual components are given as examples C to G.
- the pure polyvinyl alcohol is compared.
- the polymer mixtures 8 to 11 according to the invention show better thread closure or adhesive strength values and better abrasion resistance than the associated individual components.
- Table 3 Adhesive strength of the polymer mixtures 8 to 11 according to the invention in comparison to corresponding individual components example Chemical composition Thread closure M 0 M 200 C.
- Table 4 shows the results of the determination of the stability and viscosity of the polymer mixtures 8, 9 and 10 according to the invention.
- the comparative mixtures were prepared from one of the individual components A or B, polyvinyl alcohol and water and from the individual component F.
- the polymer mixtures 8 to 10 according to the invention are stable to the mixtures with the individual components A and B.
- Table 4 Stability and viscosity of the polymer mixtures 8 to 10 according to the invention in comparison with mixtures of individual components with a low polyvinyl alcohol content Methacrylate example used Acrylate / copolymer PVA content [%] Stability of the mixture Viscosity of the 15% liquor A 2nd Separation after 4 days 70/50 B 4th Separation after 7 days 80/50 C. 10th no separation 120/110 D 19th no separation 235/275 E 25th no separation 215/225
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Description
Die vorliegende Erfindung betrifft Copolymerisate auf der Basis von C₁-C₈-Alkylacrylaten und/oder -methacrylaten, erhältlich durch radikalische Emulsions- oder Lösungspolymerisation von
- A) 50 bis 95 Gew.-% eines C₁-C₈-Alkylacrylates und/oder -methacrylates,
- B) 5 bis 20 Gew.-% einer ungesättigten Carbonsäure und/oder eines ungesättigten Carbonsäureanhydrids,
- C) 0 bis 20 Gew.-% weiterer wasserlöslicher Comonomerer und
- D) 0 bis 10 Gew.-% sonstiger Comonomerer in Gegenwart von
- E) 2 bis 60 Gew.-Teilen Polyvinylalkohol pro 100 Gew.-Teile des Monomerengemisches aus A) bis D).
- A) 50 to 95% by weight of a C₁-C₈ alkyl acrylate and / or methacrylate,
- B) 5 to 20% by weight of an unsaturated carboxylic acid and / or an unsaturated carboxylic anhydride,
- C) 0 to 20% by weight of further water-soluble comonomers and
- D) 0 to 10% by weight of other comonomers in the presence of
- E) 2 to 60 parts by weight of polyvinyl alcohol per 100 parts by weight of the monomer mixture from A) to D).
Außerdem betrifft die Erfindung die mit Alkalimetall-, Erdalkalimetall- und Ammoniumsalzen vollständig oder partiell neutralisierten Copolymerisate, ein Verfahren zur Herstellung der Copolymerisate, deren Verwendung als Mittel zum vorübergehenden Oberflächenschutz von Form-Körpern und Flächengebilden und als Schlichtemittel für die Verarbeitung von Stapelfaser- und Filamentgarnen sowie diese Schlichtemittel.In addition, the invention relates to the copolymers completely or partially neutralized with alkali metal, alkaline earth metal and ammonium salts, a process for the preparation of the copolymers, their use as a means for the temporary surface protection of shaped bodies and flat structures and as a sizing agent for the processing of staple fiber and filament yarns as well as these sizing agents.
Weiterhin betrifft die Erfindung Schlichtemittel aus den beschriebenen Acrylat- und/oder Methacrylatcopolymeren, Polyvinylalkohol, üblichen Zusatzstoffen und vollständig oder partiell neutralisierte, Sulfo- und/oder Carboxylgruppen enthaltenden, in Salzform wasserlöslichen Polyestern aus nichtaromatischen C₂-C₆-Diolen und Gemischen aromatischer Dicarbonsäuren und aromatischer Tricarbonsäuren und/oder -sulfodicarbonsäuren sowie die Verwendung dieser Schlichtemittel für die Verarbeitung von Filamentgarnen.Furthermore, the invention relates to sizing agents from the described acrylate and / or methacrylate copolymers, polyvinyl alcohol, customary additives and completely or partially neutralized, sulfo and / or carboxyl group-containing, salt-form water-soluble polyesters of non-aromatic C₂-C₆ diols and mixtures of aromatic dicarboxylic acids and aromatic Tricarboxylic acids and / or sulfodicarboxylic acids and the use of these sizing agents for the processing of filament yarns.
Durch Emulsionspolymerisation in Gegenwart von Schutzkolloiden wie Polyvinylalkohol hergestellte Copolymerisate auf der Basis von Alkylacrylaten und/oder -methacrylaten mit untergeordneten Mengen weiterer Comonomerer wie ungesättigten Carbonsäuren, z.B. Acrylsäure, sind aus diversen Veröffentlichungen bekannt.Copolymers prepared by emulsion polymerization in the presence of protective colloids such as polyvinyl alcohol and based on alkyl acrylates and / or methacrylates with minor amounts of other comonomers such as unsaturated carboxylic acids, e.g. Acrylic acid, are known from various publications.
In diesen Copolymerisaten, die sich vornehmlich als Bindemittel für Dispersionsfarben und als Klebstoffe eignen, ist der Anteil der ungesättigten Carbonsäure mit maximal 5 % (GB 1 278 813) oder mit 1 % (DE-A 3 111 602) sehr gering.In these copolymers, which are primarily suitable as binders for emulsion paints and as adhesives, the proportion of unsaturated carboxylic acid with a maximum of 5% (GB 1 278 813) or with 1% (DE-A 3 111 602) very low.
Ist der Anteil der ungesättigten Carbonsäure höher, so enthalten die Copolymerisate andererseits mit maximal 7 % (US-A 3 876 596), mit maximal 5 % (US-A 4 670 505) oder mit maximal 2 % (US-A 4 265 796) nur sehr wenig Polyvinylalkohol als Schutzkolloid.If the proportion of unsaturated carboxylic acid is higher, the copolymers on the other hand contain a maximum of 7% (US Pat. No. 3,876,596), a maximum of 5% (US Pat. No. 4,670,505) or a maximum of 2% (US Pat. No. 4,265,796) ) very little polyvinyl alcohol as a protective colloid.
Diese Copolymerisate sind für manche Zwecke aber nur bedingt geeignet.However, these copolymers are only of limited use for some purposes.
Aus Ullmann, Bd. 23, S. 16 (1983) sind Copolymerisate auf der Basis von Acrylat- und/oder Methacrylatcopolymeren bekannt, die als Schlichtemittel empfohlen werden.Ullmann, vol. 23, p. 16 (1983) discloses copolymers based on acrylate and / or methacrylate copolymers, which are recommended as sizing agents.
Die beschriebenen Copolymerisate weisen jedoch ein unerwünschtes Verkleben der geschlichteten Filamentfäden auf und erfahren bei der Neutralisation einen großen Viskositätszuwachs.However, the copolymers described have an undesired sticking of the sized filament threads and experience a large increase in viscosity during neutralization.
Aus der JP-A-62/288076 sind Aufzeichnungsmaterialien für Tintenstrahldrucker bekannt. Die Aufzeichnungsmaterialien werden beispielsweise durch Beschichten von Folien aus Kunststoff mit einer wäßrigen Beschichtungsmasse hergestellt, die als wesentliche Bestandteile ein Pigment und einen Binder enthält. Der Binder besteht aus einem Polymer, das durch Reaktion von Polyvinyl-alkohol mit Methylmethacrylat und Acrylsäure hergestellt wird. Das Polymer enthält 3 bis 20 Gew.-% Acrylsäure und das Verhältnis von Polyvinylalkohol zu Methylmethacrylat beträgt 95 : 5 bis 10 : 90.From JP-A-62/288076 recording materials for ink jet printers are known. The recording materials are produced, for example, by coating plastic films with an aqueous coating composition which contains a pigment and a binder as essential constituents. The binder consists of a polymer that is produced by reacting polyvinyl alcohol with methyl methacrylate and acrylic acid. The polymer contains 3 to 20 wt .-% acrylic acid and the ratio of polyvinyl alcohol to methyl methacrylate is 95: 5 to 10: 90.
Aus der GB-A-1 438 449 ist die Emulsionspolymerisation von Acrylaten, Methacrylaten und Butadien in Gegenwart von hydrolysierten Vinylacetat/Alkalimetall-Olefinsulfonat-Copolymerisaten bekannt. Die Acrylate und Methacrylate können auch in Mischung mit Acrylsäure oder Methacrylsäure copolymerisiert werden. Die so erhältlichen wäßrigen Polymerdispersionen können beispielsweise als Klebstoff, Beschichtungsmittel, extilbehandlungsmittel oder Papierhilfsmittel verwendet werden.GB-A-1 438 449 discloses the emulsion polymerization of acrylates, methacrylates and butadiene in the presence of hydrolyzed vinyl acetate / alkali metal olefin sulfonate copolymers. The acrylates and methacrylates can also be copolymerized in a mixture with acrylic acid or methacrylic acid. The aqueous polymer dispersions obtainable in this way can be used, for example, as an adhesive, coating agent, exquisite treatment agent or paper auxiliary.
Der vorliegenden Erfindung liegt die Aufgabe zugrunde, neue Schlichtemittel zur Verfügung zu stellen.The object of the present invention is to provide new sizing agents.
Die Aufgabe wird erfindungsgemäß gelöst mit der Verwendung von Copolymerisaten, die erhältlich sind durch radikalische Emulsions- oder Lösungspolymerisation von
- A) 50 bis 95 Gew.-% eines C₁-C₈-Alkylacrylates und/oder -methacrylates,
- B) 5 bis 20 Gew.-% einer ungesättigten Carbonsäure und/oder eines ungesättigten Carbonsäureanhydrids,
- C) 0 bis 20 Gew.-% weiterer wasserlöslicher Comonomerer und
- D) 0 bis 10 Gew.-% sonstiger Comonomerer
in Gegenwart von - E) 2 bis 60 Gew.-Teilen Polyvinylalkohol pro 100 Gew.-Teile des Monomerengemisches aus A) bis D)
- A) 50 to 95% by weight of a C₁-C₈ alkyl acrylate and / or methacrylate,
- B) 5 to 20% by weight of an unsaturated carboxylic acid and / or an unsaturated carboxylic anhydride,
- C) 0 to 20% by weight of further water-soluble comonomers and
- D) 0 to 10% by weight of other comonomers
in the presence of - E) 2 to 60 parts by weight of polyvinyl alcohol per 100 parts by weight of the monomer mixture from A) to D)
Weiterhin wurden Schlichtemittel aus den beschriebenen Acrylat-und/oder Methacrylatcopolymeren, Polyvinylalkohol, üblichen Zusatzstoffen und vollständig oder partiell neutralisierten Sulfo- und/oder Carboxylgruppen enthaltenden, in Salzform wasserlöslichen Polyestern aus nichtaromatischen C₂-C₆-Diolen und Gemischen aromatischer Dicarbonsäuren und aroatischer Tricarbonsäuren und/oder -Sulfodicarbonsäuren gefunden.Sizing agents from the described acrylate and / or methacrylate copolymers, polyvinyl alcohol, customary additives and completely or partially neutralized sulfo and / or carboxyl groups containing salt-water-soluble polyesters from non-aromatic C₂-C₆ diols and mixtures of aromatic dicarboxylic acids and Croatian tricarboxylic acids and / or -sulfodicarboxylic acids found.
Die erfindungsgemäß zu verwendenden Copolymerisate werden aus 50 bis 95 Gew.-%, vorzugsweise 70 bis 80 Gew.-% eines C₁-C₈-Alkylacrylates und/oder -methacrylates als Komponente A und 5 bis 20 Gew.-% einer ungesättigten Carbonsäure als Komponente B in Gegenwart von 2 bis 60 Gew.-Teilen, vorzugsweise 10 bis 40 Gew.-Teilen Polyvinylalkohol, bezogen auf 100 Gew.-Teile A und B, hergestellt.The copolymers to be used according to the invention are from 50 to 95 wt .-%, preferably 70 to 80 wt .-% of a C₁-C₈ alkyl acrylate and / or methacrylate as component A and 5 to 20 wt .-% of an unsaturated carboxylic acid as a component B in the presence of 2 to 60 parts by weight, preferably 10 to 40 parts by weight of polyvinyl alcohol, based on 100 parts by weight of A and B.
Außerdem können die erfindungsgemäß zu verwendenden Copolymerisate aus bis zu 20 Gew.-% weiteren wasserlöslichen Comonomeren als Komponente C und aus bis zu 10 Gew.-% sonstigen Comonomeren als Komponente D mitaufgebaut sein.In addition, the copolymers to be used according to the invention can also be built up from up to 20% by weight of further water-soluble comonomers as component C and from up to 10% by weight of other comonomers as component D.
Als Komponente A eignen sich C₁-C₈-Alkylacrylate und/oder -methacrylate.As component A are C₁-C₈ alkyl acrylates and / or methacrylates.
Besonders bevorzugte Komponenten A sind Methyl- und n-Butylacylat und/oder -methacrylat.Particularly preferred components A are methyl and n-butyl acylate and / or methacrylate.
Bevorzugt sind Ethyl-, n-Propyl-, iso-Propyl-, iso-Butyl-, sec.-Butyl-, tert.-Butylacrylat bzw. -methacrylat.Ethyl, n-propyl, iso-propyl, iso-butyl, sec-butyl, tert-butyl acrylate or methacrylate are preferred.
Daneben sind n-Pentyl-, n-Hexyl-, 2-Ethylhexyl-, n-Heptyl- und n-Octylacrylat bzw. -methacrylat zu nennen.In addition, n-pentyl, n-hexyl, 2-ethylhexyl, n-heptyl and n-octyl acrylate or methacrylate are mentioned.
Als Komponente B kommen ungesättigte Carbonsäuren in Betracht vornehmlich die Acrylsäure und Methacrylsäure.As component B, unsaturated carboxylic acids come into consideration primarily acrylic acid and methacrylic acid.
Weiterhin eignen sich die Crotonsäure, Maleinsäure, Fumarsäure, Itaconsäure und die Anhydride der ungesättigten Carbonsäuren.Crotonic acid, maleic acid, fumaric acid, itaconic acid and the anhydrides of unsaturated carboxylic acids are also suitable.
Zusätzliche wasserlösliche Comonomere als Komponente C sind vor allem Acrylamid, Methacrylamid, Allylalkohol und ganz besonders Acrylnitril und Natriumvinylsulfonat.Additional water-soluble comonomers as component C are, above all, acrylamide, methacrylamide, allyl alcohol and very particularly acrylonitrile and sodium vinyl sulfonate.
Für die Komponente D kommen sonstige Comonomere in Betracht, bevorzugt Vinylaromaten wie Styrol, Vinylacetat, Vinylpropionat, N-Vinylpyrrolidon und die Ester von ungesättigten Dicarbonsäuren wie der Di-n-butylester der Maleinsäure.Other comonomers are suitable for component D, preferably vinyl aromatics such as styrene, vinyl acetate, vinyl propionate, N-vinylpyrrolidone and the esters of unsaturated dicarboxylic acids such as the di-n-butyl ester of maleic acid.
Die als Komponente E verwendeten Polyvinylalkohole haben vorzugsweise einen Polymerisationsgrad von 200 bis 2000 und einen Hydrolysegrad von 75 bis 99 mol-%. Die restlichen 1 bis 25 mol-% entfallen auf Acetat- oder Propionatgruppen des für die Herstellung des Polyvinylalkohols vorzugsweise verwendeten Polyvinylacetats bzw. -propionats.The polyvinyl alcohols used as component E preferably have a degree of polymerization of 200 to 2000 and a degree of hydrolysis of 75 to 99 mol%. The remaining 1 to 25 mol% are accounted for by acetate or propionate groups of the polyvinyl acetate or propionate preferably used for the production of the polyvinyl alcohol.
Zur Herstellung einer Filamentschlichte sind Polyvinylalkohole mit einem Polymerisationsgrad von 300 bis 2000 (entsprechend einer Standardviskosität von 3 bis 25 mPa·s) und einem Verseifungsgrad von 86 bis 90 mol-% bevorzugt.For the production of a filament size, polyvinyl alcohols with a degree of polymerization of 300 to 2000 (corresponding to a standard viscosity of 3 to 25 mPa · s) and a degree of saponification of 86 to 90 mol% are preferred.
Die erfindungsgemäß zu verwendenden Copolymerisate werden durch radikalische Lösungspolymerisation, vorzugsweise durch radikalische Emulsionspolymerisation in wäßriger Lösung hergestellt.The copolymers to be used according to the invention are prepared by free-radical solution polymerization, preferably by free-radical emulsion polymerization in aqueous solution.
Als Initiatoren für die radikalisch ablaufende Polymerisationsreaktion können die üblichen Peroxo- oder Azoverbindungen, auch in Kombination mit Reduktionsmitteln, zweckmäßigerweise in Mengen von 0,5 bis 2,0 Gew.-%, bezogen auf das Gewicht der Monomeren, eingesetzt werden.The usual peroxo or azo compounds, also in combination with, can be used as initiators for the radical polymerization reaction Reducing agents, advantageously in amounts of 0.5 to 2.0 wt .-%, based on the weight of the monomers.
Als bevorzugte Initiatoren sind Dibenzoylperoxid, tert.-Butylperpivalat, tert.-Butylper-2-ethylhexanoat, Di-tert.-butylperoxid, tert.-Butylhydroperoxid, 2,5-Dimethyl-2,5-di(tert.-butylperoxy)hexan, Cumolhydroperoxid und 4,4'-Azobisisobutyronitril zu nennen.Preferred initiators are dibenzoyl peroxide, tert-butyl perpivalate, tert-butyl per-2-ethylhexanoate, di-tert-butyl peroxide, tert-butyl hydroperoxide, 2,5-dimethyl-2,5-di (tert-butyl peroxy) hexane To name cumene hydroperoxide and 4,4'-azobisisobutyronitrile.
Bevorzugte Reduktionsmittel sind Hydrazin, Natriumsulfit, Natriumhydrogensulfit, Kaliumsulfit, Kaliumhydrogensulfit, Ammoniumsulfit und Ammoniumhydrogensulfit, die in Mengen von 0,005 bis 2,0 Gew.-% eingesetzt werden.Preferred reducing agents are hydrazine, sodium sulfite, sodium hydrogen sulfite, potassium sulfite, potassium hydrogen sulfite, ammonium sulfite and ammonium hydrogen sulfite, which are used in amounts of 0.005 to 2.0% by weight.
Bevorzugte Emulgatoren sind anionische Emulgatoren wie Laurylsulfat, p-n-Nonylphenol, p-n-Decylphenol, Natriumstearat, Kaliumoleat und vor allem C₁₅-Paraffinsulfonat. Als nichtionische Emulgatoren eignen sich vorzugsweise die Oxethylierungsprodukte des Laurylalkohols, Oleylalkohols, Stearylalkohols, Ölsäure- und Stearinamids, Oleylamids sowie der Stearin- und Ölsäure mit einem Oxethylierungsgrad von 3 bis 20. Ferner kommen auch kationische Emulgatoren wie Ammonium-, Phosphonium- und Sulfoniumverbindungen mit mindestens einer langen aliphatischen Kohlenwasserstoffkette als hydrophoben Molekülteil in Betracht.Preferred emulsifiers are anionic emulsifiers such as lauryl sulfate, p-n-nonylphenol, p-n-decylphenol, sodium stearate, potassium oleate and especially C₁₅ paraffin sulfonate. Suitable nonionic emulsifiers are preferably the oxyethylation products of lauryl alcohol, oleyl alcohol, stearyl alcohol, oleic acid and stearic amide, oleyl amide and stearic and oleic acid with a degree of oxyethylation of 3 to 20. Furthermore, cationic emulsifiers such as ammonium, phosphonium and sulfonium compounds are also suitable a long aliphatic hydrocarbon chain as a hydrophobic part of the molecule.
Die für eine Emulsionspolymerisation wichtigen Emulgatoren werden in Mengen von 0,1 bis 2,0 Gew.-% eingesetzt.The emulsifiers important for emulsion polymerization are used in amounts of 0.1 to 2.0% by weight.
Zur Steuerung der Molekularmasse können Regler zugesetzt werden. Besonders wichtig ist die Mitverwendung eines Reglers bei größeren Mengen Polyvinylalkohol, da es ohne einen Regler zur Bildung hochviskoser, nicht fließfähiger Lösungen kommen kann, die als Schlichtemittel weniger in Betracht kommen.Regulators can be added to control the molecular mass. It is particularly important to use a regulator with larger quantities of polyvinyl alcohol, since without a regulator it is possible to form highly viscous, non-flowable solutions that are less suitable as sizing agents.
Bevorzugte Regler sind Tetrachlorkohlenstoff, Tetrabromkohlenstoff, Benzylbromid, Trichlorbrommethan und Butylmercaptan, die im allgemeinen in Mengen von 0,1 bis 5 Gew.-% eingesetzt werden.Preferred regulators are carbon tetrachloride, carbon tetrabromide, benzyl bromide, trichlorobromomethane and butyl mercaptan, which are generally used in amounts of 0.1 to 5% by weight.
Besonders gute Ergebnisse erzielt man mit tert. -Dodecylmercaptan als Regler in Mengen von 0,2 bis 1,0 Gew.-% in Kombination mit 1,0 bis 1,5 Gew.-% einer Peroxoverbindung als Initiator.Particularly good results are achieved with tert. -Dodecyl mercaptan as a regulator in amounts of 0.2 to 1.0% by weight in combination with 1.0 to 1.5% by weight of a peroxo compound as an initiator.
Im allgemeinen führt man die Polymerisation bei 20 bis 95°C vorzugsweise bei 65 bis 90°C durch.In general, the polymerization is carried out at 20 to 95 ° C., preferably at 65 to 90 ° C.
Zweckmäßigerweise wird die Umsetzung bei Normaldruck vorgenommen, jedoch kann man auch bei vermindertem oder leicht erhöhtem Druck arbeiten, also etwa im Bereich von 0,5 bis 5 bar.The reaction is expediently carried out at normal pressure, but it is also possible to work under reduced or slightly increased pressure, that is to say in the range from 0.5 to 5 bar.
Die Reaktionszeiten betragen normalerweise 1 bis 5, meistens 2 bis 3 Stunden.The reaction times are usually 1 to 5, usually 2 to 3 hours.
Verfahrenstechnisch geht man nach dem Emulsions-Zulaufverfahren in der Regel so vor, daß man eine wäßrige Lösung aus einem Teil der Initiatoren, Emulgatoren und Regler auf die Reaktionstemperatur erhitzt und die Monomeren in gleichen oder wechselnden Anteilen, vorzugsweise kontinuierlich zuführt. Es ist auch möglich, einen Teil der Monomeren bevorzugt 4 bis 20 Gew.-% mitvorzulegen, die Polymerisation zu starten und erst nach etwa 10 bis 30 Minuten mit dem Zulauf der Hauptmenge des Monomerengemisches zu beginnen.In terms of process engineering, the emulsion feed process is generally carried out in such a way that an aqueous solution of some of the initiators, emulsifiers and regulators is heated to the reaction temperature and the monomers are fed in the same or changing proportions, preferably continuously. It is also possible to add a portion of the monomers, preferably 4 to 20% by weight, to start the polymerization and to start adding the majority of the monomer mixture after about 10 to 30 minutes.
Der Polyvinylalkohol kann zeitgleich oder zeitversetzt mit den Monomeren zugegeben werden, bevorzugt werden Mengen bis zu 10 Gew.-% in der wäßrigen Lösung vorgelegt. Die restlichen Anteile der Initiatoren, Emulgatoren und Regler werden kontinuierlich oder intermittierend zugesetzt.The polyvinyl alcohol can be added at the same time or with a time lag with the monomers; amounts of up to 10% by weight are preferably introduced in the aqueous solution. The remaining portions of the initiators, emulsifiers and regulators are added continuously or intermittently.
Nach beendetem Zulauf setzt man die Polymerisation zweckmäßigerweise unter Zusatz weiterer Initiatormengen noch etwa für eine Zeit von 1 Stunde fort, um Restmonomerengehalte abzusenken.After the feed has ended, the polymerization is expediently continued, with the addition of further amounts of initiator, for a period of about 1 hour in order to lower residual monomer contents.
Zur Herstellung der Schlichtemittel überführt man die Copolymerisate bevorzugt bei Temperaturen zwischen 50 und 85°C in ihre Natrium-, Calcium-, Magnesium-, Ammonium- oder die C₁-C₄-Alkylammoniumsalze. Im allgemeinen beträgt der Anteil der Salze mindestens 50 %.To prepare the sizing agents, the copolymers are preferably converted into their sodium, calcium, magnesium, ammonium or C₁-C₄-alkylammonium salts at temperatures between 50 and 85 ° C. In general, the proportion of the salts is at least 50%.
Sollen die Schlichtemittel zur Ausrüstung von Filamentgarnen dienen, so behandelt man den wäßrigen Latex bevorzugt mit wäßrigem Ammoniak.If the sizing agents are used to finish filament yarns, the aqueous latex is preferably treated with aqueous ammonia.
Stapelfaserschlichten erhält man vorzugsweise durch Zugabe von Natronlauge, Natriumcarbonat oder Natriumhydrogencarbonat zum wäßrigen Latex.Staple fiber sizing is preferably obtained by adding sodium hydroxide solution, sodium carbonate or sodium hydrogen carbonate to the aqueous latex.
Man kann die so erhältlichen Lösungen unmittelbar oder zusammen mit weiteren Komponenten als Schlichtemittel für Polyester-, Celluloseacetat-, Polyamid-, Viskose-, Baumwolle-, Baumwolle/Polyester-, Viskose/Polyesterund für Polyester/Wolle-Fasern verwenden.The solutions thus obtainable can be used directly or together with other components as sizing agents for polyester, cellulose acetate, polyamide, viscose, cotton, cotton / polyester, viscose / polyester and for polyester / wool fibers.
Besonders gut geeignet sind Schlichtemittel aus
- a) 20 bis 60 Gew.-%, vorzugsweise 40 bis 60 Gew.-% eines definitionsgemäßen, vollständig oder partiell neutralisierten Acrylat- und/oder Methacrylatcopolymers,
- b) 10 bis 40 Gew.-%, vorzugsweise 10 bis 25 Gew.-% Polyvinylalkohol mit einem bevorzugten Hydrolysegrad von 85 bis 90 mol-%,
- c) 20 bis 60 Gew.-%, vorzugsweise 20 bis 50 Gew.-% eines vollständig oder partiell neutralisierten, Sulfo- und/oder Carboxylgruppen enthaltenden, in Salzform wasserlöslichen Polyesters aus einem nichtaromatischen C₂-C₆-Diol und einem Gemisch einer aromatischen Dicarbonsäure und einer aromatischen Tricarbonsäure und/oder -Sulfodiccarbonsäure und
- d) 0 bis 10 Gew.-% üblicher Zusatzstoffe.
- a) 20 to 60% by weight, preferably 40 to 60% by weight, of a fully or partially neutralized acrylate and / or methacrylate copolymer as defined,
- b) 10 to 40% by weight, preferably 10 to 25% by weight, of polyvinyl alcohol with a preferred degree of hydrolysis of 85 to 90 mol%,
- c) 20 to 60 wt .-%, preferably 20 to 50 wt .-% of a completely or partially neutralized, sulfo and / or carboxyl-containing, salt-form water-soluble polyester from a non-aromatic C₂-C₆ diol and a mixture of an aromatic dicarboxylic acid and an aromatic tricarboxylic acid and / or sulfodiccarboxylic acid and
- d) 0 to 10% by weight of conventional additives.
Die als Komponente c) definierten Polyester sind bekannt oder nach bekannten Methoden erhältlich (Ullmann, Bd. 23, S. 17 (1983).The polyesters defined as component c) are known or can be obtained by known methods (Ullmann, Vol. 23, p. 17 (1983).
Man gewinnt sie durch Kondensation von nichtaromatischen C₂-C₆-Diolen wie Diethylenglykol oder 1,4-Hydroxymethylcyclohexan und einem Gemisch einer aromatischen Dicarbonsäure wie iso-Phthalsäure oder Terephthalsäure und einer aromatischen Tricarbonsäure und/oder -Sulfodicarbonsäure wie Trimellithsäure und/oder Sulfoisophthalsäure.It is obtained by condensing non-aromatic C₂-C₆ diols such as diethylene glycol or 1,4-hydroxymethylcyclohexane and a mixture of an aromatic dicarboxylic acid such as isophthalic acid or terephthalic acid and an aromatic tricarboxylic acid and / or sulfodicarboxylic acid such as trimellitic acid and / or sulfoisophthalic acid.
Bevorzugt werden Polyester mit Molekulargewichten von 150 000 bis 250 000 und einer Säurezahl von 40 bis 60 mg Kaliumhydroxid pro Gratis Polymer eingesetzt.Polyesters with molecular weights of 150,000 to 250,000 and an acid number of 40 to 60 mg of potassium hydroxide per free polymer are preferably used.
Als übliche Zusatzstoffe d sind zu nennen:
- Viskositätsregulatoren wie Perborate, Wasserstoffperoxid und Harnstoff;
- Schlichtefette wie sulfatierte Fette und Öle und primäre Fettalkoholsulfate;
- Netzmittel wie sulfierte Öle, Fettalkoholsulfate und aromatische Sulfonate;
- Entschäumer wie Amide oder Ester von Fettsäuren und Silicone und
- Konservierungsmittel wie Kupfersulfat, Aluminiumalaun, Borsäure, Formaldehyd und Benzoesäure.
- Viscosity regulators such as perborates, hydrogen peroxide and urea;
- Size greases such as sulfated fats and oils and primary fatty alcohol sulfates;
- Wetting agents such as sulfated oils, fatty alcohol sulfates and aromatic sulfonates;
- Defoamers such as amides or esters of fatty acids and silicones and
- Preservatives such as copper sulfate, aluminum alum, boric acid, formaldehyde and benzoic acid.
Weiterhin kommen Verdickungsmittel, Pigmente, Vernetzer, Füllstoffe, Verstärkungsmittel, Verfilmungshilfsmittel und Antioxidantien in Betracht.Thickeners, pigments, crosslinking agents, fillers, reinforcing agents, filming aids and antioxidants are also suitable.
Die erfindungsgemäßen Polymermischungen werden vorzugsweise durch Zusammengeben von Acrylat- und/oder Methacrylatcopolymeren, Polyvinylalkohol, Polyester und gegebenenfalls üblichen Zusatzstoffen als 15 bis 25 gew.-%ige Lösung hergestellt.The polymer mixtures according to the invention are preferably produced by combining acrylate and / or methacrylate copolymers, polyvinyl alcohol, polyester and optionally conventional additives as a 15 to 25% by weight solution.
Die Copolymerisate und Polymermischungen gemäß der Erfindung weisen bevorzugt K-Werte von 25 bis 120, besonders 30 bis 50, auf. Der jeweils gewünschte K-Wert läßt sich in an sich bekannter Weise durch Wahl der Polymerisationsbedingungen, in erster Linie der Polymerisat onsdauer und der Initiatorkonzentration, einstellen.The copolymers and polymer mixtures according to the invention preferably have K values of 25 to 120, particularly 30 to 50. The desired K value in each case can be set in a manner known per se by choosing the polymerization conditions, primarily the duration of the polymerization and the initiator concentration.
Die K-Werte werden nach Fikentscher, Cellulose-Chemie, Bd. 13, S. 58 bis 64 (1932) bei 25°C in 0,5 gew.-%iger Tetrahydrofuranlösung gemessen und stellen ein Maß für das Molgewicht dar.The K values are measured according to Fikentscher, Cellulose-Chemie, Vol. 13, pp. 58 to 64 (1932) at 25 ° C in 0.5% by weight tetrahydrofuran solution and represent a measure of the molecular weight.
Die Dispersionen oder Lösungen der erfindungsgemäßen Copolymerisate und Polymermischungen weisen Feststoffgehalte von vorzugsweise 20 bis 50 Gew.-% auf, die teilneutralisierten oder neutralisierten Dispersionen oder Lösungen haben vorzugsweise Feststoffgehalte von 18 bis 25 Gew.-%.The dispersions or solutions of the copolymers and polymer mixtures according to the invention have solids contents of preferably 20 to 50% by weight, the partially neutralized or neutralized dispersions or solutions preferably have solids contents of 18 to 25% by weight.
Die erfindungsgemäßen Copolymerisate finden hauptsächlich a s Schlichtemittel für die Verarbeitung von Stapelfaser- und Filamentgarnen Verwendung, die erfindungsgemäßen Polymermischungen dienen bevorzugt als Schlichtemittel für die Verarbeitung von Mikrofasergarnen, Multifilamentgarnen und texturierten oder glatten Filamentgarnen.The copolymers according to the invention are mainly used as sizing agents for processing staple fiber and filament yarns, the polymer mixtures according to the invention are preferably used as sizing agents for processing microfiber yarns, multifilament yarns and textured or smooth filament yarns.
Außerdem können sie zum vorübergehenden Oberflächenschutz von flächigen oder räumlichen Gebilden, beispielsweise Zeichnungen, Karte, Drucken, Fotos oder Bildern benutzt werden.They can also be used to temporarily protect the surface of flat or spatial structures, such as drawings, maps, prints, photos or images.
Des weiteren eignen sie sich als Papierverfestiger, Druckverdicker, Textilausrüstungsmittel und als Klebemittel.They are also suitable as paper strengthening agents, pressure thickeners, textile finishing agents and as adhesives.
Die Copolymerisate gemäß der Erfindung zeichnen sich durch ihre gute Schlichtewirkung bei gleichzeitig hoher Filmhärte und damit geringer Neigung zum Verkleben der geschlichteten Filamentfäden aus. Des weiteren zeigen sie hohe Klebkraftwerte sowie Mischungsstabilität und geringe Viskosität. Ein besonderer Vorteil dieser Copolymerisate ist die leichte Auswaschbarkeit vor der Weiterverarbeitung der Garne.The copolymers according to the invention are notable for their good sizing effect, while at the same time having a high film hardness and hence a low tendency to stick together the sized filament threads. Furthermore they show high adhesive strength values as well as mixture stability and low viscosity. A particular advantage of these copolymers is that they can be easily washed out before further processing of the yarns.
Die in den Beispielen angegebenen Viskositäten der Copolymerisate wurden in einem Brookfield-Viskosimeter bei 100 UpM und einer Temperatur von 20°C in wäßriger Lösung bei den jeweils angegebenen Konzentrationen gemessen.The viscosities of the copolymers given in the examples were measured in a Brookfield viscometer at 100 rpm and a temperature of 20 ° C. in aqueous solution at the concentrations given in each case.
Die gemäß den Methoden a) und b) hergestellten Copolymerisate wurden nach dem Verfahren der Emulsionspolymerisation in Form wäßriger Dispersionen erhalten. Nach Zugabe einer Base löste sich das in Wasser dispergierte Copolymerisat jeweils unter Bildung klarer wäßriger Copolymerisatlösungen.The copolymers prepared according to methods a) and b) were obtained in the form of aqueous dispersions by the emulsion polymerization process. After addition of a base, the copolymer dispersed in water dissolved in each case with the formation of clear aqueous copolymer solutions.
In den folgenden Beispielen 1 bis 5 wurde ein Polyvinylalkool (hergestellt durch Hydrolyse von Polyvinylacetat) mit einem Hydrolysegrad von 88 mol-% und einem Polymerisationsgrad von 400 (entsprechen einer Standardviskosität - gemessen bei 20°C an 4%igen wäßrigen Lösungen - von 4 mPa·s) verwendet.In the following Examples 1 to 5, a polyvinyl alcohol (produced by hydrolysis of polyvinyl acetate) with a degree of hydrolysis of 88 mol% and a degree of polymerization of 400 (corresponding to a standard viscosity - measured at 20 ° C. in 4% aqueous solutions - of 4 mPa · S) used.
Eine Lösung aus
842,5 g Wasser
0,36 g eines C-15-Paraffinsulfonats
1,4 g Natriumvinylsulfonat
20 g Polyvinylalkohol und
25,7 g Zulauf 2
wurde nach dem Erwärmen auf 80°C im Laufe von 2 bis 2,5 Stunden bei 85°C kontinuierlich mit den Zuläufen 1 und 2 versetzt.A solution
842.5 g water
0.36 g of a C-15 paraffin sulfonate
1.4 g sodium vinyl sulfonate
20 g polyvinyl alcohol and
25.7 g feed 2
After heating to 80 ° C., feeds 1 and 2 were continuously added over the course of 2 to 2.5 hours at 85 ° C.
846,9 g Wasser
1,96 g eines C-15-Paraffinsulfonats
0,6 g Natriumvinylsulfonat
70 g Methacrylsäure
280 g n-Butylacrylat
115 g Methylmethacrylat
35 g Acrylnitril846.9 g water
1.96 g of a C-15 paraffin sulfonate
0.6 g sodium vinyl sulfonate
70 g methacrylic acid
280 g of n-butyl acrylate
115 g methyl methacrylate
35 g acrylonitrile
250 g Wasser
7 g Natriumpersulfat.250 g water
7 g sodium persulfate.
Danach wurde 1 Stunde nachpolymerisiert, auf 55°C abgekühlt und mit 15%iger wäßriger Natronlauge bis pH 7,4 neutralisiert.The mixture was then polymerized for 1 hour, cooled to 55 ° C and neutralized to pH 7.4 with 15% aqueous sodium hydroxide solution.
Die erhaltene Lösung hatte einen Polymerisatgehalt von 20,6 Gew.-% und eine Viskosität von 2450 mPa·s bei 20°C.The solution obtained had a polymer content of 20.6% by weight and a viscosity of 2450 mPa · s at 20 ° C.
Dieses Copolymerisat wurde analog Beispiel 1 mit der folgenden Vorlage sowie den Zuläufen 1 und 2 hergestellt.
600,5 g Wasser
0,36 g eines C-15-Paraffinsulfonats
1,4 g Natriumvinylsulfonat
10 g Polyvinylalkohol
25,7 g Zulauf 2This copolymer was prepared analogously to Example 1 with the following template and feeds 1 and 2.
600.5 g water
0.36 g of a C-15 paraffin sulfonate
1.4 g sodium vinyl sulfonate
10 g polyvinyl alcohol
25.7 g feed 2
572,9 g Wasser
1,96 g eines C-15-Paraffinsulfonats
0,6 g Natriumvinylsulfonat
2 g tert.-Dodecylmercaptan
70 g Methacrylsäure
280 g n-Butylacrylat
115 g Methylmethacrylat
35 g Acrylnitril572.9 g water
1.96 g of a C-15 paraffin sulfonate
0.6 g sodium vinyl sulfonate
2 g of tert-dodecyl mercaptan
70 g methacrylic acid
280 g of n-butyl acrylate
115 g methyl methacrylate
35 g acrylonitrile
250 g Wasser
7 g Natriumpersulfat.250 g water
7 g sodium persulfate.
Die erhaltene Lösung hatte einen Polymerisatgehalt von 25,1 Gew.-% und bei 20°C eine Viskosität von 166 mPa·s.The solution obtained had a polymer content of 25.1% by weight and a viscosity of 166 mPa · s at 20 ° C.
Dieses Copolymerisat wurde analog Beispiel 1 mit der nachfolgenden Vorlage sowie den Zuläufen 1 und 2 hergestellt.
842 g Wasser
0,36 g eines C-15-Paraffinsulfonats
1,4 g Natriumvinylsulfonat
20 g Polyvinylalkohol
25,5 g Zulauf 2This copolymer was prepared analogously to Example 1 with the following template and feeds 1 and 2.
842 g water
0.36 g of a C-15 paraffin sulfonate
1.4 g sodium vinyl sulfonate
20 g polyvinyl alcohol
25.5 g feed 2
839,9 g Wasser
1,96 g eines C-15-Paraffinsulfonats
0,6 g Natriumvinylsulfonat
2 g tert.-Dodecylmercaptan
70 g Methacrylsäure
280 g n-Butylacrylat
115 g Methylmethacrylat
35 g Acrylnitril839.9 g water
1.96 g of a C-15 paraffin sulfonate
0.6 g sodium vinyl sulfonate
2 g of tert-dodecyl mercaptan
70 g methacrylic acid
280 g of n-butyl acrylate
115 g methyl methacrylate
35 g acrylonitrile
250 g Wasser
7 g Natriumpersulfat.250 g water
7 g sodium persulfate.
Die erhaltene Lösung hatte einen Polymerisatgehalt von 21,7 Gew.-% und bei 20°C eine Viskosität von 298 mPa·s.The solution obtained had a polymer content of 21.7% by weight and a viscosity of 298 mPa · s at 20 ° C.
Dieses Copolymerisat wurde analog Beispiel 1 mit der folgenden Vorlage sowie den Zuläufen 1 und 2 hergestellt.
832,5 g Wasser
0,36 g eines C-15-Paraffinsulfonats
1,4 g Natriumvinylsulfonat
25,7 g Zulauf 2This copolymer was prepared analogously to Example 1 with the following template and feeds 1 and 2.
832.5 g water
0.36 g of a C-15 paraffin sulfonate
1.4 g sodium vinyl sulfonate
25.7 g feed 2
896,9 g Wasser
333,3 g 30%ige wäßrige Lösung von Polyvinylalkohol
1,96 g eines C-15-Paraffinsulfonats
0,6 g Natriumvinylsulfonat
2 g tert.-Dodecylmercaptan
70 g Methacrylsäure
280 g n-Butylacrylat
115 g Methylmethacrylat
35 g Acrylnitril896.9 g water
333.3 g of 30% aqueous solution of polyvinyl alcohol
1.96 g of a C-15 paraffin sulfonate
0.6 g sodium vinyl sulfonate
2 g of tert-dodecyl mercaptan
70 g methacrylic acid
280 g of n-butyl acrylate
115 g methyl methacrylate
35 g acrylonitrile
250 g Wasser
7 g Natriumpersulfat.250 g water
7 g sodium persulfate.
Die erhaltene Lösung hatte einen Polymerisatgehalt von 20,3 Gew.-% und bei 20°C eine Viskosität von 1660 mPa·s.The solution obtained had a polymer content of 20.3% by weight and a viscosity of 1660 mPa · s at 20 ° C.
Dieses Copolymerisat wurde analog Beispiel 1 mit der folgenden Vorlage sowie den Zuläufen 1 und 2 hergestellt.
400,3 g Wasser
0,2 g eines C-15-Paraffinsulfonats
0,8 g Natriumvinylsulfonat
25,4 g Zulauf 2.This copolymer was prepared analogously to Example 1 with the following template and feeds 1 and 2.
400.3 g of water
0.2 g of a C-15 paraffin sulfonate
0.8 g sodium vinyl sulfonate
25.4 g feed 2.
661,7 g Wasser
500 g 30%ige wäßrige Lösung von Polyvinylalkohol
1,16 g eines C-15-Paraffinsulfonats
0,4 g Natriumvinylsulfonat
1,2 g tert.-Dodecylmercaptan
42 g Methacrylsäure
168 g n-Butylacrylat
69 g Methylmethacrylat
21 g Acrylnitril661.7 g water
500 g of 30% aqueous solution of polyvinyl alcohol
1.16 g of a C-15 paraffin sulfonate
0.4 g sodium vinyl sulfonate
1.2 g of tert-dodecyl mercaptan
42 g methacrylic acid
168 g of n-butyl acrylate
69 g methyl methacrylate
21 g acrylonitrile
250 g Wasser
4,2 g Natriumpersulfat.250 g water
4.2 g sodium persulfate.
Die erhaltene Lösung hatte einen Polymerisatgehalt von 20,5 Gew.-% und bei 20°C eine Viskosität von 1640 mPa·s.The solution obtained had a polymer content of 20.5% by weight and a viscosity of 1640 mPa · s at 20 ° C.
Als anwendungstechnische Eigenschaften der erfindungsgemäßen Copolymerisate wurden die Filmeigenschaften und als Maß für die Schlichtewirkung die Pilling-Werte sowie die Pseudokettfadenbruch-Werte ermittelt.The film properties and the pilling values and the pseudo warp thread break values were determined as the application properties of the copolymers according to the invention and as a measure of the sizing effect.
Zur Ermittlung der Filmeigenschaften werden mechanische Eigenschaften wie Elastizität sowie Homogenität und Zähigkeit der Filme geprüft.To determine the film properties, mechanical properties such as elasticity and homogeneity and toughness of the films are tested.
Zur Bestimmung der Filmeigenschafen wurden aus den Polymerlösungen gemäß den Beispielen 1 bis 5 2 mm dicke Folien hergestellt. Anschließend wurden diese Filme für die Dauer von 3 Stunden bei 80°C getrocknet und danach 24 Stunden bei 65 % bzw. 80 % relativer Feuchtigkeit und 20°C gehalten.To determine the properties of the film, 2 to 2 mm thick films were produced from the polymer solutions according to Examples 1 to 5. These films were then dried at 80 ° C. for 3 hours and then kept at 65% or 80% relative humidity and 20 ° C. for 24 hours.
- a) der Pilling-Werte und
- b) der Pseudo-Kettfadenbruch-Werte
Die Prüfung der Schlichtewirkung erfolgt auf dem Reutlinger Webtester, der die Belastung der Kettgarne beim Webvorgang simuliert, indem geschlichtete Garne unter einer bestimmten Spannung mittels Metallstiften wiederholt mechanisch beansprucht werden (J. Trauter u. R. Vialon, Textil Praxis International 1985, 1201). Die Anzahl dieser Beanspruchungen, bei der eine bestimmte Schädigung des Garns festzustellen ist, stellt ein Maß für die Qualität des Schlichtemittels dar.
- a) the pilling values and
- b) the pseudo warp thread break values
The sizing effect is tested on the Reutlingen weaving tester, which simulates the load on the warp yarns during the weaving process by repeatedly mechanically stressing sized yarns under a certain tension using metal pins (J. Trauter and R. Vialon, Textil Praxis International 1985, 1201). The number of these stresses, at which a certain damage to the yarn can be determined, represents a measure of the quality of the sizing agent.
- a) die Pilling-Werte unda) the pilling values and
- b) die Pseudo-Kettfadenbruch-Werte.b) the pseudo warp thread break values.
- a) Der Pilling-Wert ist derjenige Wert, bei dem die Bildung eines Knötchens an einem bestimmten Garn zu beobachten ist.a) The pilling value is the value at which the formation of a nodule on a particular yarn can be observed.
- b) Der Pseudo-Kettfadenbruch-Wert ist derjenige Wert, bei dem ein bestimmtes Garn erschlafft.b) The pseudo warp thread break value is the value at which a particular yarn slackens.
Hohe Pilling- und Pseudo-Kettfadenbruch-Werte bedeuten eine gute Schlichtewirkung.High pilling and pseudo warp thread break values mean a good sizing effect.
Zur Bestimmung der Schlichtewirkung wurden Garne aus Polyester/Baumwolle im Gewichtsverhältnis 65 : 35 bei Raumtemperatur mit 15%igen Flotten der Copolymeren auf einer Laborschlichtmaschine (DE-PS 2 714 897) geschlichtet. Anschließend wurden die geschlichteten Garne für die Dauer von 24 Stunden bei 68 % relativer Feuchtigkeit und 20°C gehalter.To determine the sizing effect, yarns of polyester / cotton in a weight ratio of 65:35 were sized at room temperature with 15% liquors of the copolymers on a laboratory sizing machine (DE-PS 2 714 897). The sized yarns were then held at 68% relative humidity and 20 ° C for 24 hours.
Die Tabelle 1 zeigt die Ergebnisse der Prüfungen A und B auf die Filmeigenschaften und die Schlichtewirkung. Die erfindungsgemäßen Copolymerisate 1 bis 5 sind vollkommen zäh, elastisch und homogen und zeigen bezüglich der Schlichtewirkung hohe Pilling- und Pseudo-Kettfadenbruch-Werte.
In den folgenden Beispielen 6 und 7 wurde ein Polyvinylalkolol (hergestellt durch Hydrolyse von Polyvinylacetat) mit einem Hydrolysegrad von 88 mol-% und einem Polymerisationsgrad von 500 (entsprechend einer Standardviskosität - gemessen bei 20°C an 4%igen wäßrigen Lösungen - von 5 mPa·s) verwendet.In Examples 6 and 7 below, a polyvinyl alcohol (produced by hydrolysis of polyvinyl acetate) with a degree of hydrolysis of 88 mol% and a degree of polymerization of 500 (corresponding to a standard viscosity - measured at 20 ° C. in 4% strength aqueous solutions - of 5 mPa · S) used.
Dieses Copolymerisat wurde analog Beispiel 1 mit der folgend in Vorlage sowie den Zuläufen 1 und 2 hergestellt. Die Neutralisation erfolgte jedoch mit 25%igem wäßrigem Ammoniak.
873,5 g Wasser
0,36 g eines C-15-Paraffinsulfonats
1,4 g Natriumvinylsulfonat
25,7 g Zulauf 2This copolymer was prepared analogously to Example 1 with the following in the template and feeds 1 and 2. However, the neutralization was carried out with 25% aqueous ammonia.
873.5 g water
0.36 g of a C-15 paraffin sulfonate
1.4 g sodium vinyl sulfonate
25.7 g feed 2
738,9 g Wasser
475 g 20%ige wäßrige Polyvinylalkohol-Lösung
1,96 g eines C-15-Paraffinsulfonats
0,6 g Natriumvinylsulfonat
70 g Methacrylsäure
250 g n-Butylacrylat
25 g n-Butylmethacrdylat
120 g Methylmethacrylat
15 g Styrol
20 g Acrylnitril738.9 g water
475 g 20% aqueous polyvinyl alcohol solution
1.96 g of a C-15 paraffin sulfonate
0.6 g sodium vinyl sulfonate
70 g methacrylic acid
250 g n-butyl acrylate
25 g n-butyl methacrylate
120 g methyl methacrylate
15 g styrene
20 g acrylonitrile
250 g Wasser
7 g Natriumpersulfat.250 g water
7 g sodium persulfate.
Die erhaltene Lösung hatte einen Polymerisatgehalt von 20,7 Gew.-% und bei 20°C eine Viskosität von 1800 mPa·s.The solution obtained had a polymer content of 20.7% by weight and a viscosity of 1800 mPa · s at 20 ° C.
Dieses Copolymerisat wurde analog Beispiel 6 mit der folgenden Vorlage sowie den Zuläufen 1 und 2 hergestellt.
873,5 g Wasser
0,36 g eines C-15-Paraffinsulfonats
1,4 g Natriumsulfonat
25,7 g Zulauf 2This copolymer was prepared analogously to Example 6 with the following template and feeds 1 and 2.
873.5 g water
0.36 g of a C-15 paraffin sulfonate
1.4 g sodium sulfonate
25.7 g feed 2
945,9 g Wasser
166,6 g 30%ige wäßrige Polyvinylalkohol-Lösung
1,96 g eines C-15-Paraffinsulfonats
0,6 g Natriumvinylsulfonat
2 g tert.-Dodecylmercaptan
70 g Methacrylsäure
280 g n-Butylacrylat
115 g Methylmethacrylat
35 g Acrylnitril945.9 g water
166.6 g 30% aqueous polyvinyl alcohol solution
1.96 g of a C-15 paraffin sulfonate
0.6 g sodium vinyl sulfonate
2 g of tert-dodecyl mercaptan
70 g methacrylic acid
280 g of n-butyl acrylate
115 g methyl methacrylate
35 g acrylonitrile
250 g Wasser
7 g Natriumpersulfat.250 g water
7 g sodium persulfate.
Die erhaltene Lösung hatte einen Polymerisatgehalt von 19,6 Gew.-% und bei 20°C eine Viskosität von 152 mPa·s.The solution obtained had a polymer content of 19.6% by weight and a viscosity of 152 mPa · s at 20 ° C.
Als anwendungstechnische Eigenschaften der erfindungsgemäßer Copolymerisate wurden der Fadenschluß und die Blocking-Neigung ermittelt.The thread closure and the tendency to blocking were determined as the application properties of the copolymers according to the invention.
Der Fadenschluß ist ein Maß für die Güte einer Schlichte in bezug auf den Schutz und die Stabilisierung des Fadens. Die Bestimmung des Fadenschlusses erfolgt mit dem Shirley-Filamentcounter, indem der Filamentfaden vor und nach dem Schlichten durchgeschnitten wird und aus den beim Schneiden gezählten Impulsen die Anzahl der freien, unverklebten Einzelfilamente ermittelt wird.The thread closure is a measure of the quality of a size in relation to the protection and stabilization of the thread. The Shirley filament counter is used to determine the thread closure by cutting the filament thread before and after finishing and determining the number of free, unglued individual filaments from the pulses counted during cutting.
Das Rohgarn besitzt einen Manra-Wert von 100, d.h. 100 % der Einzelfilamente sind unverklebt. Je niedriger der Manra-Wert, desto mehr Einzelfilamente sind an der Schnittstelle verklebt und desto besser sind der Fadenschluß sowie die Fadenhaftung und damit der erzielbare Webnutzeffekt.The raw yarn has a manra value of 100, i.e. 100% of the individual filaments are unglued. The lower the manra value, the more individual filaments are glued to the interface and the better the thread closure and the thread adhesion and thus the achievable weaving effect.
Zur Bestimmung des Fadenschlusses wurden Testgarne aus Polyester-Filament, glatt, dtex 50 f 18 mit 6 % Schlichteauflage verwendet, die sowohl direkt mit dem Shirley-Filamentcounter gemessen wurden (Manra-Wert M0 in Tabelle 2), als auch vor der Messung auf dem Reutlinger Webtester 200 Beanspruchungszyklen ausgesetzt waren (Manra-Wert M200 in Tabelle 2).To determine the thread closure, test yarns made of polyester filament, smooth, dtex 50 f 18 with 6% size layer were used, which were both measured directly with the Shirley filament counter (Manra value M0 in Table 2), as well as 200 stress cycles were exposed before the measurement on the Reutlingen web tester (Manra value M200 in Table 2).
Gute Klebkraftwerte und guter Fadenschluß sind bei M200-Werten unter 50 und bei einer möglichst geringen Differenz zwischen den MO- und M200-Wer-ten gegeben.Good adhesive strength values and good thread closure are given with M200 values below 50 and with the smallest possible difference between the MO and M200 values.
Als Blocking wird ein unerwünschtes Verkleben der geschlichieten Filamentfäden bezeichnet.Blocking is an undesired sticking of the cut filament threads.
Zur Bestimmung der Blocking-Neigung wurden geschlichtete Filamentbündel mit einer Schlichteauflage von 6 bis 7 Gew.-% zwischen zwei Glasplatten von 5 x 5 cm Größe unter Druck eines aufgesetzten Gewichtes von 1 kg bei 65 % relativer Feuchtigkeit und 21°C für die Dauer von 3 Tagen gelagert.To determine the blocking tendency, sized filament bundles with a size of 6 to 7% by weight were placed between two glass plates of 5 x 5 cm in size under pressure of an attached weight of 1 kg at 65% relative humidity and 21 ° C. for the duration of Stored for 3 days.
Die Tabelle 2 zeigt die Ergebnisse der Prüfungen A und B sowie den Anteil an Polyvinylalkohol in den Copolymerisaten der Beispiele 6 und 7.Table 2 shows the results of tests A and B and the proportion of polyvinyl alcohol in the copolymers of Examples 6 and 7.
Die erfindungsgemäßen Copolymerisate 6 und 7 zeigen einen guten Fadenschluß ohne Blocking-Neigung.
Dieses Copolymerisat wurde analog Beispiel 6 mit der folgenden Vorlage sowie den Zuläufen 1 und 2 hergestellt.
734,5 g Wasser
0,36 g eines C-15-Paraffinsulfonats
1,4 g Natriumvinylsulfonat
10,0 g Polyvinylalkohol
107,8 g Zulauf 1This copolymer was prepared analogously to Example 6 with the following template and feeds 1 and 2.
734.5 g water
0.36 g of a C-15 paraffin sulfonate
1.4 g sodium vinyl sulfonate
10.0 g polyvinyl alcohol
107.8 g feed 1
572,9 g Wasser
1,96 g eines C-15-Paraffinsulfonats
0,6 g Natriumvinylsulfonat
2,0 g tert.-Dodecylmercaptan
70,0 g Methacrylsäure
280,0 g n-Butylacrylat
115,0 g Methylmethacrylat
35,0 g Acrylnitril572.9 g water
1.96 g of a C-15 paraffin sulfonate
0.6 g sodium vinyl sulfonate
2.0 g of tert-dodecyl mercaptan
70.0 g methacrylic acid
280.0 g of n-butyl acrylate
115.0 g methyl methacrylate
35.0 g acrylonitrile
250 g Wasser
7,0 g Natriumpersulfat.250 g water
7.0 g sodium persulfate.
Die erhaltene Lösung hatte einen Polymerisatgehalt von 24,2 Gew.-% und bei 20°C eine Viskosität vom 110 mPa·s.The solution obtained had a polymer content of 24.2% by weight and a viscosity of 110 mPa · s at 20 ° C.
Dieses Copolymerisat wurde analog Beispiel 6 mit der folgenden Vorlage sowie den Zuläufen 1 und 2 hergestellt.
873,5 g Wasser
0,36 g eines C-15-Paraffinsulfonats
1,4 g Natriumvinylsulfonat
20 g Polyvinylalkohol
138,1 g Zulauf 2This copolymer was prepared analogously to Example 6 with the following template and feeds 1 and 2.
873.5 g water
0.36 g of a C-15 paraffin sulfonate
1.4 g sodium vinyl sulfonate
20 g polyvinyl alcohol
138.1 g feed 2
875,9 g Wasser
1,96 g eines C-15-Paraffinsulfonats
0,6 g Natriumvinylsulfonat
2 g tert.-Dodecylmercaptan
280 g n-Butylacrylat
115 g Methylmethacrylat
35 g Acrylnitril
70 g Methacrylsäure875.9 g water
1.96 g of a C-15 paraffin sulfonate
0.6 g sodium vinyl sulfonate
2 g of tert-dodecyl mercaptan
280 g of n-butyl acrylate
115 g methyl methacrylate
35 g acrylonitrile
70 g methacrylic acid
250 g Wasser
7 g Natriumpersulfat.250 g water
7 g sodium persulfate.
Die erhaltene Lösung hatte einen Polymerisatgehalt von 20,1 Gew.-% und bei 20°C eine Viskosität von 128 mPa·s.The solution obtained had a polymer content of 20.1% by weight and a viscosity of 128 mPa · s at 20 ° C.
Dieses Copolymerisat wurde analog Beispiel 6 mit der folgenden Vorlage sowie den Zuläufen 1 und 2 hergestellt.
873,5 g Wasser
0,36 g eines C-15-Paraffinsulfonats
1,4 g Natriumvinylsulfonat
161,7 g Zulauf 1This copolymer was prepared analogously to Example 6 with the following template and feeds 1 and 2.
873.5 g water
0.36 g of a C-15 paraffin sulfonate
1.4 g sodium vinyl sulfonate
161.7 g feed 1
945,9 g Wasser
166,6 g 30%ige wäßrige Polyvinylalkohollösung
1,96 g eines C-15-Paraffinsulfonats
0,6 g Natriumvinylsulfonat
2 g tert.-Dodecylmercaptan
280 g n-Butylacrylat
115 g Methylmethacrylat
35 g Acrylnitril
70 g Methacrylsäure945.9 g water
166.6 g of 30% aqueous polyvinyl alcohol solution
1.96 g of a C-15 paraffin sulfonate
0.6 g sodium vinyl sulfonate
2 g of tert-dodecyl mercaptan
280 g of n-butyl acrylate
115 g methyl methacrylate
35 g acrylonitrile
70 g methacrylic acid
250 g Wasser
7 g Natriumpersulfat.250 g water
7 g sodium persulfate.
Die erhaltene Lösung hatte einen Polymerisatgehalt von 19,6 Gew.-% und bei 20°C eine Viskosität von 152 mPa·s.The solution obtained had a polymer content of 19.6% by weight and a viscosity of 152 mPa · s at 20 ° C.
Dieses Copolymerisat wurde analog Beispiel 6 mit der folgenden Vorlage sowie den Zuläufen 1 und 2 hergestellt.
873,5 g Wasser
0,36 g eines C-15-Paraffinsulfonats
1,4 g Natriumvinylsulfonat
174,7 g Zulauf 1This copolymer was prepared analogously to Example 6 with the following template and feeds 1 and 2.
873.5 g water
0.36 g of a C-15 paraffin sulfonate
1.4 g sodium vinyl sulfonate
174.7 g feed 1
768,9 g Wasser
475 g 20%ige wäßrige Polyvinylalkohollösung
1,96 g eines C-15-Paraffinsulfonats
0,6 g Natriumvinylsulfonat
2 g tert.-Dodecylmercaptan
280 g n-Butylacrylat
115 g Methylmethacrylat
35 g Acrylnitril
70 g Methacrylsäure768.9 g water
475 g 20% aqueous polyvinyl alcohol solution
1.96 g of a C-15 paraffin sulfonate
0.6 g sodium vinyl sulfonate
2 g of tert-dodecyl mercaptan
280 g of n-butyl acrylate
115 g methyl methacrylate
35 g acrylonitrile
70 g methacrylic acid
250 g Wasser
7 g Natriumpersulfat.250 g water
7 g sodium persulfate.
Die erhaltene Lösung hatte einen Polymerisatgehalt von 20,4 Gew.-% und bei 20°C eine Viskosität von 1620 mPa·s.The solution obtained had a polymer content of 20.4% by weight and a viscosity of 1620 mPa · s at 20 ° C.
Dieses Copolymerisat wurde analog Beispiel 6 mit der folgenden Vorlage sowie den Zuläufen 1 und 2 hergestellt.
873,5 g Wasser
0,36 g eines C-15-Paraffinsulfonats
1,4 g Natriumvinylsulfonat
190 g Zulauf 1This copolymer was prepared analogously to Example 6 with the following template and feeds 1 and 2.
873.5 g water
0.36 g of a C-15 paraffin sulfonate
1.4 g sodium vinyl sulfonate
190 g feed 1
770,9 g Wasser
625 g 20%ige wäßrige Polyvinylalkohollösung
1,96 g eines C-15-Paraffinsulfonats
0,6 g Natriumvinylsulfonat
2 g tert.-Dodecylmercaptan
280 g n-Butylacrylat
115 g Methylmethacrylat
35 g Acrylnitril
70 g Methacrylsäure770.9 g water
625 g of 20% aqueous polyvinyl alcohol solution
1.96 g of a C-15 paraffin sulfonate
0.6 g sodium vinyl sulfonate
2 g of tert-dodecyl mercaptan
280 g of n-butyl acrylate
115 g methyl methacrylate
35 g acrylonitrile
70 g methacrylic acid
768 g Wasser
7 g Natriumpersulfat.768 g water
7 g sodium persulfate.
Die erhaltene Lösung hatte einen Polymerisatgehalt von 20,6 Gew.-% und bei 20°C eine Viskosität von 1400 mPa·s.The solution obtained had a polymer content of 20.6% by weight and a viscosity of 1400 mPa · s at 20 ° C.
Dieser Polyester mit -COOH-Gruppen wurde durch Kondensation von
1 Mol Diethylenglykol
0,54 Mol Cyclohexandimethanol (1,4-Hydroxymethylcyclohexan)
1,12 Mol iso-Phthalsäure
0,2 Mol Terephthalsäure
0,23 Mol Trimellithsäureanhydrid
hergestellt. Die Neutralisation erfolgte mit Ammoniak/Triethanolamin im Verhältnis 6 : 4.This polyester with -COOH groups was obtained by condensation of
1 mole of diethylene glycol
0.54 mol cyclohexanedimethanol (1,4-hydroxymethylcyclohexane)
1.12 moles of isophthalic acid
0.2 mole of terephthalic acid
0.23 mole trimellitic anhydride
manufactured. The neutralization was carried out with ammonia / triethanolamine in a ratio of 6: 4.
Dieser Polyester mit -SO₃H-Gruppen wurde durch Kondensation von
0,86 Mol Diethylenglykol
0,2 Mol Cyclohexandimethanol (1,4-Hydroxymethylcyclohexan)
0,23 Mol iso-Phthalsäure
0,70 Mol Terephthalsäure
0,13 Mol Sulfoisophthalsäure
hergestellt. Die Neutralisation erfolgte mit Natriumsalz bis zu pH 5,6.This polyester with -SO₃H groups was by condensation of
0.86 mole of diethylene glycol
0.2 mol cyclohexanedimethanol (1,4-hydroxymethylcyclohexane)
0.23 mole of isophthalic acid
0.70 mole of terephthalic acid
0.13 mole of sulfoisophthalic acid
manufactured. The neutralization was carried out with sodium salt up to pH 5.6.
Die erfindungsgemäßen Polymermischungen 8 bis 11 wurden in der Kälte in einem solchen Verhältnis aus
- Schlichtelösung aus einer der Einzelkomponenten C bis E
- Polyvinylalkohol und Wasser und
- Polyesterschlichtelösung aus einer der Einzelkomponenten F oder G
- 21 % Polyvinylalkohol als Summe aus dem Polyvinylalkoho anteil der Einzelkomponente und separat zugesetztem Polyvinylalkohol
- 50 % Acrylat/Methacrylat-Copolymer und
- 29 % Polyester
- Sizing solution from one of the individual components C to E
- Polyvinyl alcohol and water and
- Polyester sizing solution from one of the individual components F or G
- 21% polyvinyl alcohol as the sum of the polyvinyl alcohol portion of the individual component and separately added polyvinyl alcohol
- 50% acrylate / methacrylate copolymer and
- 29% polyester
Als anwendungstechnische Eigenschaft der erfindungsgemäßen Polymermischungen wurden die Fadenschlußwerte ermittelt.The thread closure values were determined as a performance characteristic of the polymer mixtures according to the invention.
Die Tabelle 3 zeigt die Ergebnisse dieser Prüfung sowie die chemische Zusammensetzung in den Polymermischungen 8 bis 11. Zum Vergleich sind als Beispiele C bis G die entsprechenden Einzelkomponenten angegeben. Außerdem ist der reine Polyvinylalkohol gegenübergestellt.Table 3 shows the results of this test and the chemical composition in polymer mixtures 8 to 11. For comparison, the corresponding individual components are given as examples C to G. In addition, the pure polyvinyl alcohol is compared.
Die erfindungsgemäßen Polymermischungen 8 bis 11 zeigen bessere Fadenschluß- bzw. Klebkraftwerte sowie bessere Abriebfestigkeit als die zugehörigen Einzelkomponenten.
Als Vergleich zu den erfindungsgemäßen Polymermischungen wurden solche mit den Einzelkomponenten A und B gegenübergestellt. Tabelle 4 zeigt die Ergebnisse der Bestimmung der Stabilität und Viskosität der erfindungsgemäßen Polymermischungen 8, 9 und 10. Die vergleichenden Mischungen wurden aus einer der Einzelkomponente A oder B, Polyvinylalkohol und Wasser sowie der Einzelkomponente F hergestellt.As a comparison to the polymer mixtures according to the invention, those with the individual components A and B were compared. Table 4 shows the results of the determination of the stability and viscosity of the polymer mixtures 8, 9 and 10 according to the invention. The comparative mixtures were prepared from one of the individual components A or B, polyvinyl alcohol and water and from the individual component F.
Die erfindungsgemäßen Polymermischungen 8 bis 10 sind gegenüber den Mischungen mit den Einzelkomponenten A und B mischungsstabil.
Claims (6)
- The use of copolymers which are obtainable by free radical emulsion or solution polymerization ofA) from 50 to 95 % by weight of a C₁-C₈-alkyl acrylate and/or methacrylate,B) from 5 to 20 % by weight of an unsaturated carboxylic acid and/or anhydride,C) from 0 to 20 % by weight of further water-soluble comonomers, andD) from 0 to 10 % by weight of other comonomersin the presence ofE) from 2 to 60 parts by weight of a polyvinyl alcohol per 100 parts by weight of the monomer mixture of A) to D)and which are completely or partially present as alkali metal, alkaline earth metal or ammonium salts, as size for stapel fiber and filament yarns.
- A use as claimed in claim 1, wherefor the copolymers are obtainable by free radical emulsion or solution polymerization ofA) from 70 to 80 % by weight of a C₁-C₈-alkyl acrylate and/or methacrylate,B) from 5 to 20 % by weight of an unsaturated carboxylic acid and/or anhydride,C) from 0 to 20 % by weight of further water-soluble comonomers, andD) from 0 to 10 % by weight of other comonomersin the presence ofE) from 10 to 40 parts by weight of a polyvinyl alcohol per 100 parts by weight of the monomer mixture of A) to D).
- A use as claimed in claim 1 or 2, wherefor at least 50% of the copolymers are present as sodium, calcium, magnesium, ammonium or C₁- to C₄-alkylammonium salt.
- A size comprisinga) from 20 to 60 % of the partially or completely neutralized copolymer to be used as claimed in claim 1,b) from 10 to 40 % by weight of a polyvinyl alcohol,c) from 20 to 60 % by weight of a completely or partially neutralized, sulfo- and/or carboxylcontaining polyester which is formed from a nonaromatic C₂-C₆-diol and a mixture of an aromatic dicarboxylic acid and an aromatic tricarboxylic and/or sulfodicarboxylic acid and is water-soluble in salt form, andd) from 0 to 10 % by weight of customary additives.
- A size comprisinga) from 40 to 60 % of a copolymer to be used as claimed in claim 3,b) from 10 to 25 % by weight of a polyvinyl alcohol,c) from 20 to 50 % by weight of a completely or partially neutralized, sulfo- and/or carboxylcontaining polyester which is formed from a nonaromatic C₂-C₆-diol and a mixture of an aromatic dicarboxylic acid and an aromatic tricarboxylic and/or sulfodicarboxylic acid and is water-soluble in salt form, andd) from 0 to 10 % by weight of customary additives.
- The use of the size of claim 4 or 5 for the processing of microfiber yarns, multifilament yarns and textured or flat filament yarns.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE4010563 | 1990-04-02 | ||
DE4010563A DE4010563A1 (en) | 1990-04-02 | 1990-04-02 | COPOLYMERISATE BASED ON C (DOWN ARROW) 1 (DOWN ARROW) -C (DOWN ARROW) 8 (DOWN ARROW) ALKYL ACRYLATES AND / OR METHACRYLATES |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0450437A2 EP0450437A2 (en) | 1991-10-09 |
EP0450437A3 EP0450437A3 (en) | 1992-04-08 |
EP0450437B1 true EP0450437B1 (en) | 1995-06-07 |
Family
ID=6403582
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP91104620A Expired - Lifetime EP0450437B1 (en) | 1990-04-02 | 1991-03-23 | Copolymers based on C1-C8-alkyl-acrylates and/or methacrylates, process for their preparation and their use |
Country Status (6)
Country | Link |
---|---|
US (1) | US5231145A (en) |
EP (1) | EP0450437B1 (en) |
JP (1) | JPH04224811A (en) |
DE (2) | DE4010563A1 (en) |
ES (1) | ES2073057T3 (en) |
PT (1) | PT97218B (en) |
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CA2220419A1 (en) * | 1992-04-01 | 1996-11-14 | Henkel Corporation | Composition and process for treating metal |
DE4213514A1 (en) * | 1992-04-24 | 1993-10-28 | Basf Ag | Use of water-soluble or water-dispersible suspension polymers as textile fiber sizing agents |
CA2110448A1 (en) * | 1992-12-08 | 1994-06-09 | Helen H.Y. Pak-Harvey | Redispersible acrylic polymer powder for cementitious compositions |
JP3416194B2 (en) * | 1993-04-26 | 2003-06-16 | 株式会社ジーシー | Separation material for denture base |
DE4318033C2 (en) * | 1993-05-29 | 1996-08-29 | Hoechst Ag | Copolymers containing carboxyl groups in aqueous dispersion form or redispersible powder form and their water-soluble salts, processes for their preparation and their use as thickeners in aqueous preparations |
US5405653A (en) * | 1994-02-28 | 1995-04-11 | E. I. Du Pont De Nemours And Company | Poly(vinyl alcohol)starch blends for textile sizes with improved ability to be desized |
US5362515A (en) * | 1994-02-28 | 1994-11-08 | E. I. Du Pont De Nemours And Company | Poly(vinyl alcohol)copolymer sizes having high capacity to be desized |
US5436293A (en) * | 1994-02-28 | 1995-07-25 | E. I. Du Pont De Nemours And Company | Poly(vinyl alcohol) polymer blend textile sizes with improved ability to be desized |
DE4407842A1 (en) * | 1994-03-09 | 1995-09-14 | Huels Chemische Werke Ag | Protective colloid-stabilized polyacrylate dispersions |
GB9422093D0 (en) * | 1994-11-02 | 1994-12-21 | Zeneca Ltd | Rheology modifier for solvent-based coatings |
DE4447359C5 (en) * | 1994-12-21 | 2009-01-02 | ALTERFIL Nähfaden GmbH | Bauschiges sewing thread |
US5741871A (en) * | 1996-06-14 | 1998-04-21 | Air Products And Chemicals, Inc. | Acrylic emulsions prepared in the presence of fully hydrolyzed poly (vinyl alcohol) |
KR100448933B1 (en) * | 1996-07-01 | 2004-11-26 | 가부시키가이샤 구라레 | Fiber liner |
US5753036A (en) * | 1997-04-21 | 1998-05-19 | Air Products And Chemicals, Inc. | Poly(vinyl alcohol) stabilized acrylic polymer modified hydraulic cement systems |
JP2002529603A (en) * | 1998-07-01 | 2002-09-10 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | Poly (vinyl alcohol) copolymer ionomer, its preparation, and its use in fabric size |
US6114417A (en) * | 1998-10-16 | 2000-09-05 | Cytec Technology Corp. | Paper sizing agents and methods |
FR2785629B1 (en) * | 1998-11-10 | 2000-12-22 | Coatex Sa | POLYMERIC COMPOSITION FOR WATER RETENTION AND ACTIVATOR OF OPTICAL BRIGHTENERS, COATING SAUCES FOR PAPER, AND SHEETS OF COATED PAPER THUS OBTAINED |
DE19857897A1 (en) * | 1998-12-15 | 2000-06-21 | Basf Ag | Process for the preparation of aqueous polymer dispersions |
DE19960863A1 (en) * | 1999-12-17 | 2001-06-28 | Basf Ag | Polymers stabilized with polyvinyl alcohol to enhance the optimal brightening of coating materials |
ITSV20020051A1 (en) * | 2002-10-11 | 2004-04-12 | Allaix Roberto C O Ferrania S P A Uff Brevetti | SUMMARY OF A COPOLYMER IN THE FORM OF PARTICLES CONTAINING HYDROFILE FUNCTIONALITY. |
KR100659455B1 (en) * | 2004-11-09 | 2006-12-19 | 주식회사 엘지화학 | Additive for vinyl chloride resin and vinyl chloride resin composition having thereof |
JP4888853B2 (en) | 2009-11-12 | 2012-02-29 | 学校法人慶應義塾 | Method for improving visibility of liquid crystal display device, and liquid crystal display device using the same |
EP2558638A1 (en) * | 2010-04-15 | 2013-02-20 | Basf Se | Treatment of textile and formulations suitable therefor |
MX342229B (en) | 2010-06-21 | 2016-09-21 | Basf Se | Sound damping compositions and methods for application and use. |
KR101699497B1 (en) | 2010-06-22 | 2017-01-24 | 도요보 가부시키가이샤 | Liquid crystal display device, polarizing plate and polarizer protective film |
CN106094091B (en) | 2011-05-18 | 2019-03-15 | 东洋纺株式会社 | Polarizer and polaroid protective film |
US10175494B2 (en) | 2011-05-18 | 2019-01-08 | Toyobo Co., Ltd. | Polarizing plate suitable for liquid crystal display device capable of displaying three-dimensional images, and liquid crystal display device |
CN102505485B (en) * | 2011-10-20 | 2013-08-21 | 天津工业大学 | Hair slip prevention finishing agent and finishing method for rabbit hair fabric |
CN104520738B (en) * | 2012-08-07 | 2017-02-01 | 东洋纺株式会社 | Polyester film for polarizer protection, polarizing plate and liquid crystal display device |
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US3909477A (en) * | 1973-06-27 | 1975-09-30 | Dow Chemical Co | Warp-sizing compositions and yarns sized therewith |
DE2714897C3 (en) * | 1977-04-02 | 1981-12-03 | Basf Ag, 6700 Ludwigshafen | Use of water-soluble alkaline earth salts of polymers of acrylic acid or methacrylic acid as sizing agents |
DE2842719A1 (en) * | 1978-09-30 | 1980-04-10 | Basf Ag | METHOD FOR PRODUCING AQUEOUS POLYACRYLATE DISPERSIONS WITH IMPROVED FLOW BEHAVIOR |
DE3167114D1 (en) * | 1980-11-24 | 1984-12-13 | Akzo Nv | A sized multifilament yarn of an aromatic polyamide, a yarn package, a woven fabric and a process for making said yarn |
DE3111602A1 (en) * | 1981-03-24 | 1982-10-07 | Wacker-Chemie GmbH, 8000 München | COPOLYMERISATE OF INCREASED WATER RESISTANCE, METHOD FOR THEIR PRODUCTION AND THEIR USE |
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-
1990
- 1990-04-02 DE DE4010563A patent/DE4010563A1/en not_active Withdrawn
-
1991
- 1991-03-20 JP JP3056719A patent/JPH04224811A/en active Pending
- 1991-03-23 EP EP91104620A patent/EP0450437B1/en not_active Expired - Lifetime
- 1991-03-23 ES ES91104620T patent/ES2073057T3/en not_active Expired - Lifetime
- 1991-03-23 DE DE59105640T patent/DE59105640D1/en not_active Expired - Lifetime
- 1991-04-01 PT PT97218A patent/PT97218B/en not_active IP Right Cessation
- 1991-04-02 US US07/679,275 patent/US5231145A/en not_active Expired - Fee Related
Non-Patent Citations (1)
Title |
---|
WORLD PATENTS INDEX Derwent Publications Ltd., London, GB; AN 76-06468X & JP-B-50 039 685 * |
Also Published As
Publication number | Publication date |
---|---|
PT97218A (en) | 1992-01-31 |
DE59105640D1 (en) | 1995-07-13 |
PT97218B (en) | 1998-07-31 |
US5231145A (en) | 1993-07-27 |
ES2073057T3 (en) | 1995-08-01 |
EP0450437A3 (en) | 1992-04-08 |
EP0450437A2 (en) | 1991-10-09 |
DE4010563A1 (en) | 1991-10-10 |
JPH04224811A (en) | 1992-08-14 |
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